U.S. patent number 7,094,448 [Application Number 10/330,920] was granted by the patent office on 2006-08-22 for spray pack.
This patent grant is currently assigned to Asahi Kasei Chemical Corporation. Invention is credited to Hideki Amakawa, Hirofumi Ono.
United States Patent |
7,094,448 |
Ono , et al. |
August 22, 2006 |
**Please see images for:
( Certificate of Correction ) ** |
Spray pack
Abstract
Disclosed is a spray pack for use in forming a uniform, stable
spray coating, comprising a spray container device and, packed
therein, a spraying composition comprising a liquid dispersion
medium and, dispersed therein, particulate cellulose having an
average degree of polymerization (DP) of not more than 300 and an
average particle diameter of not more than 10 .mu.m, wherein the
composition has a cellulose content of from 0.1 to 5.0% by weight,
and wherein the composition exhibits a maximum viscosity value
(.eta..sub.max) of 1.times.10.sup.3 mPas or more in the
viscosity-shear stress curve obtained, with respect to the
composition, using a cone-plate type rotating viscometer in a shear
rate region of from 1.times.10.sup.-3 s.sup.-1 to 1.times.10.sup.2
s.sup.-1 and at 25.degree. C. A method for forming a uniform,
stable spray coating by using the above-mentioned spray pack is
also disclosed.
Inventors: |
Ono; Hirofumi (Numazu,
JP), Amakawa; Hideki (Fuji, JP) |
Assignee: |
Asahi Kasei Chemical
Corporation (Tokyo, JP)
|
Family
ID: |
33421229 |
Appl.
No.: |
10/330,920 |
Filed: |
December 27, 2002 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20040123775 A1 |
Jul 1, 2004 |
|
Current U.S.
Class: |
427/427.4;
106/15.05; 106/162.9; 106/163.01; 106/200.3; 106/203.1; 106/204.01;
106/204.3; 424/401; 424/407; 424/43; 424/46; 424/47; 424/59;
514/781; 536/1.11; 536/123.1; 536/123.12; 536/124; 536/126; 536/56;
536/57 |
Current CPC
Class: |
A61K
8/046 (20130101); A61K 8/731 (20130101); A61K
9/7015 (20130101); A61Q 19/00 (20130101); A61Q
19/02 (20130101); C08L 1/02 (20130101); A61K
2800/412 (20130101) |
Current International
Class: |
B05D
1/00 (20060101); C07H 1/00 (20060101); C08B
16/00 (20060101); C09D 1/00 (20060101); C09D
101/02 (20060101) |
Field of
Search: |
;106/15.05,162.9,163.01,200.3,203.1,204.01,204.3
;424/401,407,43,46,47,59,71 ;514/781
;536/56,57,1.11,123.12,126,123.1,124 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1 036 799 |
|
Sep 2000 |
|
EP |
|
9-241115 |
|
Sep 1997 |
|
JP |
|
2000-51682 |
|
Feb 2000 |
|
JP |
|
2000-229255 |
|
Aug 2000 |
|
JP |
|
2000-351726 |
|
Dec 2000 |
|
JP |
|
2001-72999 |
|
Mar 2001 |
|
JP |
|
2001-89359 |
|
Apr 2001 |
|
JP |
|
Primary Examiner: Brunsman; David
Attorney, Agent or Firm: Dickstein, Shapiro, Morin &
Oshinsky, LLP.
Claims
The invention claimed is:
1. A spray pack for use in forming a uniform, stable spray coating,
comprising a spray container device and, packed therein, a spraying
composition comprising a liquid dispersion medium and, dispersed
therein, particulate cellulose having an average degree of
polymerization (DP) of not more than 300 and an average particle
diameter of not more than 10 .mu.m, said spraying composition
having a cellulose content of from 0.1 to 5.0% by weight, wherein
said spraying composition exhibits a maximum viscosity value
(.eta..sub.max) of 1.times.10.sup.3 mPas or more in the
viscosity-shear stress curve obtained, with respect to said
composition, using a cone-plate type rotating viscometer in a shear
rate region of from 1.times.10.sup.-3 s.sup.-1 to 1.times.10.sup.2
s.sup.-1 and at 25.degree. C.
2. The spray pack according to claim 1, wherein said particulate
cellulose has an average degree of polymerization (DP) of not more
than 100, and has a cellulose I type crystal component fraction of
0.1 or less and a cellulose II type crystal component fraction of
0.4 or less, and wherein said particulate cellulose has an average
particle diameter of not more than 2 .mu.m.
3. The spray pack according to claim 1 or 2, wherein said
particulate cellulose has an average particle diameter of not more
than 1 .mu.m.
4. The spray pack according to claim 1 or 2, wherein said maximum
viscosity value (.eta..sub.max) in the viscosity-shear stress curve
is 5.times.10.sup.5 mPas or more.
5. The spray pack according to claim 1 or 2, wherein said liquid
dispersion medium comprises water and an organic solvent.
6. The spray pack according to claim 5, wherein said organic
solvent is a water-soluble alcohol.
7. The spray pack according to claim 1 or 2, which further
comprises at least one functional additive.
8. The spray pack according to claim 7, wherein at least a part of
said functional additive is an ionic compound, and wherein the
content of said ionic compound in said composition is from 0.1 to
10% by weight.
9. The spray pack according to claim 7, wherein said at least one
functional additive is selected from the group consisting of an oil
compound, a humectant, a surfactant, a metal oxide, an ultraviolet
screener, an inorganic salt, a metal powder, a gum, a dye, a
pigment, a silica compound, a latex, a water-soluble polymer, an
amino acid, a cosmetic ingredient, a pharmaceutical, an
insecticide, a deodorizer, an antimicrobial agent, an antiseptic
agent and a perfume.
10. The spray pack according to claim 1 or 2, wherein when said
spraying composition is diluted with water to have a particulate
cellulose concentration of 0.05% by weight, the resultant aqueous
composition exhibits a transmittance of 80% or more to visible rays
having a wavelength of 660 nm.
11. A method for forming a uniform, stable spray coating,
comprising: providing a spray pack comprising a spray container
device and, packed therein, a spraying composition, and actuating
said spray container device to spray said spraying composition onto
a surface, thereby forming a spray coating on said surface, said
spraying composition comprising a liquid dispersion medium and,
dispersed therein, particulate cellulose having an average degree
of polymerization (DP) of not more than 300 and an average particle
diameter of not more than 10 .mu.m, said spraying composition
having a cellulose content of from 0.1 to 5.0% by weight, wherein
said spraying composition exhibits a maximum viscosity value
(.eta..sub.max) of 1.times.10.sup.3 mPas or more in the
viscosity-shear stress curve obtained, with respect to said
composition, using a cone-plate type rotating viscometer in a shear
rate region of from 1.times.10.sup.-3 s.sup.-1 to 1.times.10.sup.2
s.sup.-1 and at 25.degree. C.
12. The method according to claim 11, wherein said particulate
cellulose has an average degree of polymerization (DP) of not more
than 100, and has a cellulose I type crystal component fraction of
0.1 or less and a cellulose II type crystal component fraction of
0.4 or less, and wherein said particulate cellulose has an average
particle diameter of not more than 2 .mu.m.
13. The method according to claim 11 or 12, wherein said
particulate cellulose has an average particle diameter of not more
than 1 .mu.m.
14. The method according to claim 11 or 12, wherein said maximum
viscosity value (.eta..sub.max) in the viscosity-shear stress curve
is 5.times.10.sup.5 mPas or more.
15. The method according to claim 11 or 12, wherein said liquid
dispersion medium comprises water and an organic solvent.
16. The method according to claim 15, wherein said organic solvent
is a water-soluble alcohol.
17. The method according to claim 11 or 12, which further comprises
at least one functional additive.
18. The method according to claim 17, wherein at least a part of
said functional additive is an ionic compound, and wherein the
content of said ionic compound in said composition is from 0.1 to
10% by weight.
19. The method according to claim 17, wherein said at least one
functional additive is selected from the group consisting of an oil
compound, a humectant, a surfactant, a metal oxide, an ultraviolet
screener, an inorganic salt, a metal powder, a gum, a dye, a
pigment, a silica compound, a latex, a water-soluble polymer, an
amino acid, a cosmetic ingredient, a pharmaceutical, an
insecticide, a deodorizer, an antimicrobial agent, an antiseptic
agent and a perfume.
20. The method according to claim 11 or 12, wherein when said
spraying composition is diluted with water to have a particulate
cellulose concentration of 0.05% by weight, the resultant aqueous
composition exhibits a transmittance of 80% or more to visible rays
having a wavelength of 660 nm.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a spray pack for use in forming a
uniform, stable spray coating, comprising a spray container device
and, packed therein, a spraying composition comprising a liquid
dispersion medium and, dispersed therein, particulate cellulose
having an average degree of polymerization (DP) of not more than
300 and an average particle diameter of not more than 10 .mu.m,
wherein the spraying composition has a cellulose content of from
0.1 to 5.0% by weight, and wherein the spraying composition
exhibits a maximum viscosity value (.eta..sub.max) of
1.times.10.sup.3 mPas or more in the viscosity-shear stress curve
obtained, with respect to the composition, using a cone-plate type
rotating viscometer in a shear rate region of from
1.times.10.sup.-3 s.sup.-1 to 1.times.10.sup.2 s.sup.-1 and at
25.degree. C. The spraying composition used in the spray pack of
the present invention is advantageous not only in that it has
excellent spraying properties and also in that, after the spraying,
the sprayed composition (coating) has excellent properties with
respect to fixation to the surface coated, anti-dripping
properties, spreadability and finish (uniformity of the coating).
Therefore, the present invention is also concerned with a method
for forming a uniform, stable spray coating, which comprises
providing a spray pack comprising a spray container device and,
packed therein, a spraying composition of the above-mentioned type;
and actuating the spray container device to spray the spraying
composition onto a surface, thereby forming a spray coating on the
surface.
2. Prior Art
In recent years, spraying products are used in a wide variety of
fields, such as the fields of skincare products, hair care
products, a medicine for external use, a medicine for oral use, an
insecticide, a fragrance, a deodorizer, an antimicrobial agent, a
sterilizer, a halitosis deodorizer, a detergent, a paint, a coating
agent for anti-fogging treatment, a coating agent for anti-static
treatment, and an antiseptic agent. A spraying product comprises a
spray container device and, packed therein, a spraying composition.
In most cases, the spraying composition packed in the spray
container device is in liquid form.
A spraying composition is desired to have the following properties:
(1) a general purpose container can be used as the spray container
device therefor, and good spraying can be performed in a wide
variety of environments; (2) after the spraying, the sprayed
composition has excellent properties with respect to fixation to
the surface coated and the uniformity of the coating; (3) the
sprayed composition is unlikely to drip even when the surface
coated is vertical or inclined; and (4) when the sprayed
composition is dried, a coating can be formed which is not only
stable but also has high safety in that skin stimulation (i.e.,
skin irritation) and the like are not exhibited. However, there is
no conventional spraying composition possessing all of these
desired properties.
In order to solve the problems of the conventional spraying
compositions, various proposals have been made.
For example, in order to solve the tasks (1) to (3) above,
Unexamined Japanese Patent Application Laid-Open Specification No.
2001-89359 proposes a method in which a polymeric thickening agent
is added to a spraying composition, thereby increasing the
viscosity of the composition. However, the following should be
noted. In the case of a conventional polymer solution as a spraying
composition, when the viscosity of the spraying composition is
increased too much by adding a thickening agent in an attempt to
prevent the dripping thereof after the spraying, it becomes
impossible to spray the composition due to the high viscosity of
the composition. Therefore, for enabling drawing up of the
composition by suction through the suction tube to the spray nozzle
and enabling the spraying of the composition, it is necessary to
decrease the viscosity of the composition by some degree. However,
such decrease in viscosity, in turn, results in a lowering of the
anti-dripping properties of the composition. Therefore, it is very
difficult to achieve a good balance of the anti-dripping properties
and the sprayability (spraying properties) of the composition.
Further, even if conditions can be found which enable the spraying
of the composition, there has conventionally been a problem in
that, due to the stringiness of the composition (characteristic of
a polymer solution), the composition upon being sprayed cannot form
desired fine particles (mist); that is, the mist-forming ability of
the composition is poor, resulting in non-uniformity of the coating
obtained, as compared to the case of a spraying composition which
does not contain a thickening agent.
Further, in order to solve the tasks (2) and (3) above, many
methods have been proposed, for example, a method in which a
surfactant is added to the composition so as to increase the
viscosity by utilizing the interactions between the micelles formed
in the aqueous phase, and a method in which the surface tension of
the sprayed composition (liquid particles) on the coated surface is
controlled (see, for example, Unexamined Japanese Patent
Application Laid-Open Specification Nos. 2001-72999 and
2000-351726). However, there is a problem, for example, in that the
compositions of these patent documents have a fluidity and
therefore cannot be sprayed when the spray container device
containing such a composition is held upside down. Therefore, the
task (1) above cannot be completely solved by these conventional
methods. Further, there are other problems, as follows. These
conventional methods cannot increase the viscosity of the
composition to a level sufficient for substantially completely
preventing the dripping after spraying. Furthermore, when a large
amount of a surfactant is added to the composition in an attempt to
increase the viscosity thereof, the surfactant is likely to
irritate the skin. Thus, the task (4) above (concerning safety) and
the like cannot be solved.
In order to solve the tasks (1) and (3) above, improvements in the
structure of the spray container device have been suggested (see,
for example, Unexamined Japanese Patent Application Laid-Open
Specification No. 2000-229255). However, this technique poses the
following problems. In the case of the use of such a spray
container device, when the spraying is performed for forming a thin
coating, the dripping after spraying can be prevented. However,
when the spraying is performed for forming a thick coating (i.e.,
when repeated sprayings are needed), there is a problem in that the
dripping of the sprayed composition occurs. In addition, in this
technique, the spray container device has a complicated structure,
so that such spray container device lacks the general-purpose
properties and the cost for producing the spray container device
becomes markedly high. Therefore, from the viewpoint of developing
a spraying composition which can be used without limitation in a
wide variety of application fields, this technique cannot be
considered as a fundamental solution to the problem of the dripping
after spraying.
In an attempt to provide a relatively well-balanced solution to all
of the tasks (1) to (4) above, Unexamined Japanese Patent
Application Laid-Open Specification Nos. Hei 9-241115 and
2000-51682 disclose a gel-like, spraying composition which
contains, as a main component, hectorite comprising hydrophilic
smectite. However, the main component of the spraying composition
is an inorganic compound which has not actually been put to use for
a time long enough to confirm its safety. Further, in the case of
this composition, a problem arises in that aggregation of hectorite
is likely to occur in a dispersion medium (such as alcohol) which
is widely used in a spraying composition, thus causing a lowering
of the spraying properties. In addition, there is a problem in that
dissolution-out of a large amount of salt contained in hectorite
occurs, and the salt is likely to induce aggregation of other
components which are sensitive to the presence of salt; this means
that the freedom of formulation of the spraying composition is
limited.
At the "Dai 13-kai Kobunshi Geru Kenkyu Toronkai (13th Forum on
Polymer Gel)" (sponsored by the Society of Polymer Science, Japan;
Jan. 17 18, 2002; pages 49 50 of the preliminary text), the present
inventors reported their finding that, although an aqueous
dispersion of the cellulose used in the present invention has
gel-like properties (exhibiting no fluidity), it has excellent
spraying properties such that it can be easily sprayed using an
ordinary spray container device, thereby exhibiting good spraying.
However, for utilizing such finding in a wide variety of fields of
industry, it was needed to find conditions under which the
gel-like, cellulose dispersion can, as well, exhibit excellent
properties with respect to stability of gel and to spraying
performance even when the cellulose dispersion is a composite
formulation additionally containing not only an alcohol but also
various types of additives.
SUMMARY OF THE INVENTION
In this situation, the present inventors have made extensive and
intensive studies with a view toward solving the above-mentioned
problems of the prior art. As a result, it has unexpectedly been
found that a spraying composition desired for the above-mentioned
object can be produced by using a cellulose dispersion which
comprises a liquid dispersion medium (such as water) and, dispersed
therein, particulate cellulose having a specific, relatively small
particle diameter. More specifically, the present inventors have
unexpectedly found that the cellulose dispersion disclosed in WO
99/28350 (corresponding to EP 1 036 799 A1) has excellent
properties with respect to spraying properties; formation and
maintenance of a foam; thixotropic properties (i.e., the ability to
exhibit a low viscosity quickly at the application of a lower shear
stress than in the case of other materials); and dispersion
stability for various compounds. Further, it has surprisingly been
found that a spraying composition which is obtained by adjusting
the viscosity of the above-mentioned cellulose dispersion to a
value within a specific range can solve all of the tasks (1) to (4)
above, and such spraying composition is also advantageous in that
it has high transparency and, after spraying and drying, can
provide a coating having high transparency. Furthermore, it has
also been found that, even when various types of liquid dispersion
mediums and functional additives are added to the spraying
composition, the composition is stable and exhibits excellent
spraying properties. Based on these findings, the present invention
has been completed.
Accordingly, it is an object of the present invention to provide a
spray pack for use in forming a uniform, stable spray coating,
which packs therein a spraying composition, wherein the spraying
composition can solve all of the tasks (1) to (4) above, i.e., a
spraying composition which has the following properties: (1) a
general purpose container can be used as the spray container device
therefor, and good spraying can be performed in a wide variety of
environments; (2) after the spraying, the sprayed composition has
excellent properties with respect to fixation to the surface coated
and the uniformity of the coating; (3) the sprayed composition is
unlikely to drip even when the surface coated is vertical or
inclined; and (4) when the sprayed composition is dried, a coating
can be formed which is not only stable but also has high safety in
that skin stimulation (i.e., skin irritation) and the like are not
exhibited.
It is another object of the present invention to provide a method
for forming a uniform, stable spray coating by using the
above-mentioned spray pack.
The foregoing and other objects, features and advantages of the
present invention will be apparent from the following detailed
description taken in connection with the accompanying drawings and
the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a graph showing the method for determining h.sub.0,
h.sub.1, h.sub.0* and h.sub.1* in a wide-angle X-ray pattern
obtained with respect to a cellulose used in the present invention
(a dried product obtained from sample A);
FIG. 2 is a graph showing the viscosity-shear rate curve obtained
with respect to a cellulose/water dispersion (used in the present
invention) having a cellulose content of 1.5% by weight (sample
S3), wherein the measurement for obtaining the curve was performed
using a cone-plate type rotating viscometer at 25.degree. C.;
and
FIG. 3 is a graph showing the method for determining a maximum
viscosity value (.eta..sub.max) in the viscosity-shear stress curve
obtained with respect to a cellulose/water dispersion (used in the
present invention) having a cellulose content of 1.5% by weight
(sample S3), wherein the measurement for obtaining the curve was
performed using a cone-plate type rotating viscometer at 25.degree.
C.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, there is provided a spray pack
for use in forming a uniform, stable spray coating, comprising a
spray container device and, packed therein, spraying composition
comprising a liquid dispersion medium and, dispersed therein,
particulate cellulose having an average degree of polymerization
(DP) of not more than 300 and an average particle diameter of not
more than 10 .mu.m,
the spraying composition having a cellulose content of from 0.1 to
5.0% by weight,
wherein the spraying composition exhibits a maximum viscosity value
(.eta..sub.max) of 1.times.10.sup.3 mPas or more in the
viscosity-shear stress curve obtained, with respect to the
composition, using a cone-plate type rotating viscometer in a shear
rate region of from 1.times.10.sup.-3 s.sup.-1 to 1.times.10.sup.2
s.sup.-1 and at 25.degree. C.
For easy understanding of the present invention, the essential
features and various preferred embodiments of the present invention
are enumerated below.
1. A spray pack for use in forming a uniform, stable spray coating,
comprising a spray container device and, packed therein, a spraying
composition comprising a liquid dispersion medium and, dispersed
therein, particulate cellulose having an average degree of
polymerization (DP) of not more than 300 and an average particle
diameter of not more than 10 .mu.m,
the spraying composition having a cellulose content of from 0.1 to
5.0% by weight,
wherein the spraying composition exhibits a maximum viscosity value
(.eta..sub.max) of 1.times.10.sup.3 mPas or more in the
viscosity-shear stress curve obtained, with respect to the
composition, using a cone-plate type rotating viscometer in a shear
rate region of from 1.times.10.sup.-3 s.sup.-1 to 1.times.10.sup.2
s.sup.-1 and at 25.degree. C.
2. The spray pack according to item 1 above, wherein the
particulate cellulose has an average degree of polymerization (DP)
of not more than 100, and has a cellulose I type crystal component
fraction of 0.1 or less and a cellulose II type crystal component
fraction of 0.4 or less, and wherein the particulate cellulose has
an average particle diameter of not more than 2 .mu.m. 3. The spray
pack according to item 1 or 2 above, wherein the particulate
cellulose has an average particle diameter of not more than 1
.mu.m. 4. The spray pack according to item 1 or 2 above, wherein
the maximum viscosity value (.eta..sub.max) in the viscosity-shear
stress curve is 5.times.10.sup.5 mPas or more. 5. The spray pack
according to item 1 or 2 above, wherein the liquid dispersion
medium comprises water and an organic solvent. 6. The spray pack
according to item 5 above, wherein the organic solvent is a
water-soluble alcohol. 7. The spray pack according to item 1 or 2
above, which further comprises at least one functional additive. 8.
The spray pack according to item 7 above, wherein at least a part
of the functional additive is an ionic compound, and wherein the
content of the ionic compound in the composition is from 0.1 to 10%
by weight. 9. The spray pack according to item 7 above, wherein the
at least one functional additive is selected from the group
consisting of an oil compound, a humectant, a surfactant, a metal
oxide, an ultraviolet screener, an inorganic salt, a metal powder,
a gum, a dye, a pigment, a silica compound, a latex, a
water-soluble polymer, an amino acid, a cosmetic ingredient, a
pharmaceutical, an insecticide, a deodorizer, an antimicrobial
agent, an antiseptic agent and a perfume. 10. The spray pack
according to item 1 or 2 above, wherein when the spraying
composition is diluted with water to have a particulate cellulose
concentration of 0.05% by weight, the resultant aqueous composition
exhibits a transmittance of 80% or more to visible rays having a
wavelength of 660 nm. 11. A method for forming a uniform, stable
spray coating, comprising:
providing a spray pack comprising a spray container device and,
packed therein, a spraying composition, and
actuating the spray container device to spray the spraying
composition onto a surface, thereby forming a spray coating on the
surface,
the spraying composition comprising a liquid dispersion medium and,
dispersed therein, particulate cellulose having an average degree
of polymerization (DP) of not more than 300 and an average particle
diameter of not more than 10 .mu.m,
the spraying composition having a cellulose content of from 0.1 to
5.0% by weight,
wherein the spraying composition exhibits a maximum viscosity value
(.eta..sub.max) of 1.times.10.sup.3 mPas or more in the
viscosity-shear stress curve obtained, with respect to the
composition, using a cone-plate type rotating viscometer in a shear
rate region of from 1.times.10.sup.-3 s.sup.-3 to 1.times.10.sup.2
s.sup.-1 and at 25.degree. C.
12. The method according to item 11 above, wherein the particulate
cellulose has an average degree of polymerization (DP) of not more
than 100, and has a cellulose I type crystal component fraction of
0.1 or less and a cellulose II type crystal component fraction of
0.4 or less, and wherein the particulate cellulose has an average
particle diameter of not more than 2 .mu.m. 13. The method
according to item 11 or 12, wherein the particulate cellulose has
an average particle diameter of not more than 1 .mu.m. 14. The
method according to item 11 or 12 above, wherein the maximum
viscosity value (.eta..sub.max) in the viscosity-shear stress curve
is 5.times.10.sup.5 mPas or more. 15. The method according to item
11 or 12 above, wherein the liquid dispersion medium comprises
water and an organic solvent. 16. The method according to item 15
above, wherein the organic solvent is a water-soluble alcohol. 17.
The method according to item 11 or 12 above, which further
comprises at least one functional additive. 18. The method
according to item 17 above, wherein at least a part of the
functional additive is an ionic compound, and wherein the content
of the ionic compound in the composition is from 0.1 to 10% by
weight. 19. The method according to item 17 above, wherein the at
least one functional additive is selected from the group consisting
of an oil compound, a humectant, a surfactant, a metal oxide, an
ultraviolet screener, an inorganic salt, a metal powder, a gum, a
dye, a pigment, a silica compound, a latex, a water-soluble
polymer, an amino acid, a cosmetic ingredient, a pharmaceutical, an
insecticide, a deodorizer, an antimicrobial agent, an antiseptic
agent and a perfume. 20. The method according to item 11 or 12
above, wherein when the spraying composition is diluted with water
to have a particulate cellulose concentration of 0.05% by weight,
the resultant aqueous composition exhibits a transmittance of 80%
or more to visible rays having a wavelength of 660 nm.
Hereinbelow, the present invention is described in detail.
Essentially, the present invention is concerned with a spray pack
comprising a spray container device and, packed therein, the
spraying composition. The spraying composition used in the present
invention is obtained by dispersing particulate cellulose in a
medium. More specifically, the spraying composition comprises a
liquid dispersion medium (selected in accordance with the purpose
of use of the composition (provided that the dispersion medium must
not be a solvent for the cellulose)) and, dispersed therein,
particulate cellulose as a viscosity modifier, wherein the
composition may further comprise an additive selected in accordance
with the purpose of use of the composition. Further, the present
invention is also concerned with a method for forming a uniform,
stable spray coating by using the above-mentioned spray pack.
The particulate cellulose used in the present invention is
described below. First, a relatively simple explanation is made on
the particulate cellulose, and next, a detailed explanation is made
on the average degree of polymerization (DP) and average particle
diameter of the cellulose used in the present invention, the
fraction of the cellulose I type crystal component, and the
fraction of the cellulose II type crystal component.
The spraying composition used in the present invention comprises
particulate cellulose having an average degree of polymerization
(DP) of not more than 300 and an average particle diameter of not
more than 10 .mu.m, and the composition has a cellulose content of
from 0.1 to 5.0% by weight. In the present invention, the term
"average degree of polymerization (DP)" means a weight average
degree of polymerization, and the term "average particle diameter"
means a volume average particle diameter.
The cellulose used in the present invention has an average degree
of polymerization (DP) of from 10 to 300, preferably from 10 to
100, more preferably from 20 to 50. When the DP is more than 300,
it is difficult to obtain a cellulose dispersion in which cellulose
is dispersed as microparticles exhibiting a high degree of
dispersion, thus leading to disadvantages in that the viscosity and
dispersion stability of the spraying composition become low. When
the DP is less than 10, most of the cellulose in the dispersion
becomes water-soluble and hence cannot form microparticles which
give high viscosity to the spraying composition used in the present
invention, thus making it difficult for the cellulose to exhibit
effects as a viscosity modifier.
The cellulose used in the present invention has an average particle
diameter of not more than 10 .mu.m, preferably not more than 2
.mu.m, more preferably not more than 1 .mu.m. The lower limit of
the average particle diameter is 0.02 .mu.m, which is close to the
lower detection limit of the method used for measuring the average
particle diameter in the present invention. When the cellulose has
an average particle diameter of more than 10 .mu.m, not only does
it become difficult to obtain the high viscosity which is
characteristic of the composition used in the present invention,
but also the thixotropic properties of the composition are
lowered.
Examples of celluloses satisfying such requirements include natural
cellulose and particulate cellulose which is obtained by subjecting
regenerated cellulose to an acid hydrolysis. It is preferred to use
a commercially available microcrystalline cellulose and a
mechanical pulverization product thereof, and it is also preferred
to use particulate cellulose of low crystallinity obtained by using
the below-mentioned method. However, with respect to the cellulose
used in the present invention, there is no particular limitation as
long as the cellulose meets the requirements mentioned above.
Hereinbelow, explanations are made on the methods for determining
the average degree of polymerization (DP) and average particle
diameter of the cellulose used in the present invention.
The average degree of polymerization (DP) of the cellulose is
determined as follows. The cellulose is dispersed in a liquid
dispersion medium (e.g., water) to obtain a cellulose dispersion.
The cellulose dispersion is dried to obtain a dried cellulose
sample. The dried cellulose sample is dissolved in cadoxene to
obtain a diluted cellulose solution (cadoxene is a solution of a
cadmium complex and has the following composition:
CdO/H.sub.2NCH.sub.2CH.sub.2NH.sub.2/NaOH/H.sub.2O=5/28/1.4/165.6
(weight ratio)). The specific viscosity of the diluted cellulose
solution is measured (at 25.degree. C.) using a Ubbelohde's
viscometer. From the specific viscosity, an intrinsic viscosity
value [.eta.] is obtained. From the intrinsic viscosity value
[.eta.], a weight average degree of polymerization (DP) is obtained
by calculation according to the following viscosity equation (1)
and the conversion equation (2):
[.eta.]=3.85.times.10.sup.-2.times.M.sub.w.sup.0.76 (1)
DP=M.sub.w/162 (2) (With respect to the method for determining the
DP, reference can be made to W. Brown and R. Wikstroem, Euro.
Polym. J., 1, (1965), pages 1 12.)
The average particle diameter of the cellulose is measured as
follows. The cellulose is dispersed in a liquid dispersion medium
(preferably, water) to obtain a cellulose dispersion. With respect
to the obtained cellulose dispersion, measurement is performed at
room temperature by means of a laser diffraction type particle size
distribution measuring apparatus (Laser Diffraction/Scatting Type
Particle Size Measuring Apparatus LA-920, manufactured and sold by
HORIBA Ltd., Japan; the lower detection limit is 0.02 .mu.m). For
measuring the average particle diameter as in the state in which
the association between the cellulose particles in the cellulose
dispersion is broken as much as possible, a sample for measurement
is prepared by the following procedure. The cellulose dispersion is
diluted with water so that the cellulose content becomes about 0.5%
by weight, to obtain a diluted cellulose dispersion. The diluted
cellulose dispersion is subjected to a treatment for increasing the
degree of dispersion, by means of a blender having a revolution
rate of not less than 15,000 rpm, for 10 minutes to thereby obtain
a sample for measurement of the average particle diameter of the
cellulose. Subsequently, this sample is fed to the flow cell of the
particle size distribution measuring apparatus and subjected to
appropriate ultrasonic treatment. Then, the particle size
distribution of the cellulose is measured (based on the particle
volume distribution calculated by the Mie scattering theoretical
formula). A volume average particle diameter is determined from the
particle size distribution. The obtained volume average particle
diameter is used as the average particle diameter of the
cellulose.
It is preferred that the particulate cellulose used in the present
invention has such a low crystallinity that the cellulose I type
crystal component fraction (x.sub.I) is 0.1 or less, more
advantageously 0, and the cellulose II type crystal component
fraction (x.sub.II) is 0.4 or less, more advantageously 0.3 or
less. The composition obtained using such particulate cellulose
having low crystallinity exhibits high transparency. It is more
preferred that such particulate cellulose having low crystallinity
has an average particle diameter of 2 .mu.m or less, more
advantageously 1 .mu.m or less. The composition obtained using such
particulate cellulose exhibits not only higher transparency, but
also viscosity increasing ability even at a relatively low
cellulose content.
Hereinbelow, the methods for determining the fractions (x.sub.I and
x.sub.II) of cellulose I type and cellulose II type crystal
components are described.
The fraction (x.sub.I) of cellulose I type crystal component is
obtained as follows. The cellulose is dispersed in a liquid
dispersion medium to obtain a cellulose dispersion. The cellulose
dispersion is dried to obtain a dried cellulose sample. The dried
cellulose sample is pulverized into a powder, and the powder is
subjected to tableting to obtain a tablet. The tablet is subjected
to wide-angle X-ray diffractometry by the reflection method (using
Rotaflex RU-300; manufactured and sold by Rigaku Corporation,
Japan) (X ray source: CuK.alpha.). In the resultant wide-angle
X-ray diffraction pattern (see FIG. 1), the absolute intensity
h.sub.0 of the peak (at 2.theta.=15.0.degree.) ascribed to the
(110) diffraction of the cellulose I type crystal, and the peak
intensity h.sub.1 corresponding to the distance between the top and
base line of the same peak are determined. From the h.sub.0 value
and the h.sub.1 value, the fraction (x.sub.I) of cellulose I type
crystal component is determined by the below-mentioned equation
(3).
The fraction (x.sub.II) of cellulose II type crystal component is
obtained as follows. In the above-mentioned wide-angle X-ray
diffraction pattern (see FIG. 1), the absolute intensity h.sub.0*
of the peak (at 2.theta.=12.6.degree.) ascribed to the (110)
diffraction of the cellulose II type crystal, and the peak
intensity h.sub.1* corresponding to the distance between the top
and base line of the same peak are determined. From the h.sub.0*
value and the h.sub.1* value, the fraction (x.sub.II) of cellulose
II type crystal component is determined by the below-mentioned
equation (4). x.sub.I=h.sub.1/h.sub.0 (3)
x.sub.II=h.sub.1*/h.sub.0* (4)
A diagram showing the method for determining x.sub.I and x.sub.II
is shown in FIG. 1.
Next, an explanation is made on the liquid dispersion medium for
dispersing the cellulose therein.
Usually, the liquid dispersion medium used in the present invention
is water. However, a water-soluble organic solvent (e.g., an
alcohol) may be used as a liquid dispersion medium. The
water-soluble organic solvent may be used in addition to or instead
of water. Further, a hydrophobic organic solvent may be used,
depending on the purpose of use of the composition. These
dispersion mediums may be used as a mixture thereof. In the present
invention, the "liquid dispersion medium" is defined as a compound
which is in liquid form at room temperature and under atmospheric
pressure and which does not directly contribute to the functions of
the composition used in the present invention. In the spraying
composition used in the present invention, the liquid dispersion
medium is used mainly for improving the dispersibility or
dissolvability of the components of the composition.
When a water-soluble organic solvent is used as the dispersion
medium, the amount of the organic solvent is from 1 to 90% by
weight, preferably from 3 to 60% by weight, more preferably from 5
to 50% by weight, based on the weight of the composition. When the
amount of the water-soluble organic solvent is less than 1% by
weight, any appreciable effect cannot be obtained by the
replacement of water with the water-soluble organic solvent. On the
other hand, since the replacement of water which binds to the
particulate cellulose is technically difficult, addition of the
water-soluble organic solvent in an amount of more than 90% by
weight is not recommendable.
Examples of water-soluble organic solvents include alkyl alcohols
having 1 to 4 carbon atoms, such as methanol, ethanol, n-propyl
alcohol, iso-propyl alcohol, n-butyl alcohol, sec-butyl alcohol,
tert-butyl alcohol, and the like; ketones or keto alcohols, such as
dimethylformamide, dimethylacetamide, acetone, diacetone alcohol,
and the like; ethers, such as tetrahydrofuran, dioxane, and the
like; alkylene glycols having an alkylene group having 2 to 6
carbon atoms, such as ethylene glycol, propylene glycol, butylene
glycol, triethylene glycol, 1,2,6-hexane triol, thiodiglycol,
hexylene glycol, diethylene glycol, and the like; cellosolves, such
as ethylene glycol monomethyl ether, ethylene glycol monoethyl
ether, and the like; Carbitols, such as diethylene glycol
monomethyl ether, diethylene glycol monoethyl ether, ethylene
glycol mono-n-butyl ether, diethylene glycol-n-butyl ether,
triethylene glycol-n-butyl ether, and the like; 1,2-alkyldiols,
such as 1,2-hexanediol, 1,2-octanediol, and the like; polyethylene
glycol; polypropylene glycol; glycerol and derivatives thereof;
N-methyl-2-pyrrolidone; 2-pyrrolidone; and
1,3-dimethyl-2-imidazolidinone. However, examples of water-soluble
organic solvents are not limited to those which are mentioned
above. In the present invention, the "water-soluble organic
solvent" is defined as an organic solvent which exhibits a
solubility in water (even if the solubility is small) and which is
used at a concentration (or in an amount) which is not more than
the solubility of the organic solvent in water.
When a mixture of water and a water-soluble organic solvent, or an
emulsion comprising water and a hydrophobic organic solvent, is
used as the liquid dispersion medium, advantages can be obtained
not only in that various types of functional additives can be
dissolved or dispersed in the liquid dispersion medium, but also in
that the drying rate of the liquid dispersion medium (after
spraying) can be adjusted easily, as compared to the case of use of
water only.
When a mixture of water and a water-soluble organic solvent is used
as the liquid dispersion medium, the weight ratio of water-soluble
organic solvent/water is from 0.01 to 9, preferably from 0.03 to 2.
When the weight ratio is less than 0.01, any appreciable effect
cannot be obtained by the replacement of water with a water-soluble
organic solvent. On the other hand, since the replacement of water
which binds to the particulate cellulose is technically difficult,
use of the water-soluble organic solvent in a weight ratio
(water-soluble organic solvent/water) of more than 9 is not
recommendable.
Further, when an emulsion comprising water and a hydrophobic
organic solvent is used as the liquid dispersion medium, the weight
ratio of hydrophobic organic solvent/water is from 0.01 to 2,
preferably from 0.03 to 1. When the weight ratio is less than 0.01,
any appreciable effect cannot be obtained by the replacement of
water with a hydrophobic organic solvent. When the weight ratio is
more than 2, use of a large amount of surfactant is necessary for
obtaining a stable emulsion, thus causing a disadvantage in that
the formulation of the spraying composition is greatly limited.
Among the above-mentioned water-soluble organic solvents, it is
preferred to use a water-soluble alcohol (such as ethanol or
ethylene glycol), that is, it is preferred to use an aqueous
solution of a water-soluble alcohol as the liquid dispersion
medium, since the use of such liquid dispersion medium makes it
possible to obtain a spraying composition having high transparency
over a relatively broad range of formulation of the components. In
the present invention, the "water-soluble alcohol" is defined as an
alcohol which exhibits a solubility in water (even if the
solubility is small) and which is used at a concentration (or in an
amount) which is not more than the solubility of the alcohol in
water.
Examples of hydrophobic organic solvents include aliphatic
hydrocarbons or derivatives thereof, such as n-pentane, n-hexane,
n-heptane, 1-butene, 1-pentene, and the like; benzene or
derivatives thereof; toluene or derivatives thereof; aromatic
hydrocarbons, such as xylene, decalin, and the like; esters, such
as ethyl acetate, propyl lactate, propyl butyrate, and the like;
and ethers, such as methyl butyl ether and the like. However, the
hydrophobic organic solvent is not limited to these examples. When
a water-insoluble hydrophobic organic solvent is used as the liquid
dispersion medium, the solvent may be emulsified by effecting an
appropriate emulsifying treatment, depending on the purpose of use
of the spraying composition. Further, a solvent (such as a
water-soluble alcohol) which is soluble in both water and a
water-insoluble hydrophobic organic solvent, may be added to water
and the water-insoluble hydrophobic organic solvent to thereby form
a homogeneous, mixed solvent comprising three or more solvents.
The composition used in the present invention comprises the
above-mentioned particulate cellulose and the above-mentioned
liquid dispersion medium. With respect to the ratio between these
components of the composition, an explanation is made below.
The cellulose content required for the composition used in the
present invention having an appropriately high viscosity varies
depending on the properties (DP, the average particle diameter and
the crystal component fraction) of the cellulose. However, the
cellulose content of the composition is generally from 0.1 to 5.0%
by weight, preferably from 0.3 to 4.0% by weight, more preferably
from 0.5 to 2.5% by weight. When the cellulose content of the
composition is less than 0.1% by weight, it is likely that the
excellent anti-dripping properties (after spraying) aimed at by the
present invention cannot be obtained. On the other hand, when the
cellulose content of the composition is more than 5.0% by weight,
the viscosity of the composition becomes extremely high, leading to
a problem in that, when the composition is packed in a spray
container, the composition is likely to contain air, making it
difficult to perform a stable spraying.
It is required that the composition used in the present invention
exhibit a maximum viscosity value (.eta..sub.max) of
1.times.10.sup.3 mPas or more in the viscosity-shear stress curve
obtained, with respect to the composition, using a cone-plate type
rotating viscometer in a shear rate region of from
1.times.10.sup.-3 s.sup.-1 to 1.times.10.sup.2 s.sup.-1 and at
25.degree. C. In FIGS. 2 and 3, as specific examples of measurement
data, there are, respectively, shown a viscosity (.eta.)-shear rate
(.gamma., i.e., gamma dot) curve and a viscosity (.eta.)-shear
stress (.pi.) curve which were obtained by measurement performed at
25.degree. C. with respect to a cellulose/water dispersion (used in
the present invention) having a cellulose content of 1.5% by weight
(sample S3).
As a cone-plate type rotating viscometer, RS-100, manufactured and
sold by Haake, Germany, was used (wherein, in the cone-plate, the
cone angle was 4.degree. and the diameter of the plate was 35 mm).
In FIG. 3, when the .pi. value is about 2 Pa or less, the .eta.
value (viscosity) is almost constant and does not depend on the
.pi. value, that is, the so-called Newtonian viscosity is
exhibited; however, when the .pi. value is more than 2 Pa, the
.eta. value (viscosity) is sharply decreased. For example, when the
.pi. value=20 Pa, the .eta. value (viscosity) is as low as only 50
mPas. This data shows the high thixotropy of the composition used
in the present invention. In addition, it should be noted that the
data of FIG. 3 also shows that the critical shear stress value
(.pi..sub.c in FIG. 3) (at which the viscosity (.eta.) exhibits a
sharp decrease) is extremely low, as compared to the case of the
viscosity (.eta.)-shear stress (.pi.) curves which are obtained,
with respect to conventional materials. That is, the composition
used in the present invention has an advantage in that,
irrespective of its extremely high viscosity, the composition
exhibits a low viscosity when only a low shear stress is applied to
the composition. By virtue of this property, the composition used
in the present invention can be drawn up by suction to the spray
nozzle through the suction tube. The data of FIG. 3 shows that
sample S3 (exhibiting a maximum viscosity value (.eta..sub.max) of
2.times.10.sup.6 mPas) exhibits a critical shear stress value
(.pi..sub.c) of 2.2 Pa (wherein sample S3 was produced in an
Example of the present specification). This data of FIG. 3 should
be compared, for example, with the data of sample H2 (general
purpose gel), which was used in a Comparative Example of the
present specification. Sample H2 is a 0.5% by weight aqueous
solution of Carbopol 940.TM. and exhibits a maximum viscosity value
(.eta..sub.max) of 3.times.10.sup.6 mPas. Although the
.eta..sub.max value (3.times.10.sup.6 mPas) of Sample H2 is at the
same level as that of sample S3, sample H2 exhibits a critical
shear stress value (.pi..sub.c) as high as 26 Pa, which is
extremely high, as compared to the .pi..sub.c value (2.2 Pa) of
sample S3.
When the composition exhibits a maximum viscosity value
(.eta..sub.max) of less than 1.times.10.sup.3 mPas, the viscosity
is too low, so that it is likely that the excellent anti-dripping
properties (after spraying) aimed at by the present invention
cannot be obtained. In cases where the spraying is performed so
that the coating density becomes relatively low, satisfactory
anti-dripping properties (after spraying) can be obtained when the
requirement that the .eta..sub.max value .gtoreq.1.times.10.sup.3
mPas is satisfied. However, in cases where the spraying is
performed so that the coating density becomes relatively high, it
is possible that satisfactory anti-dripping properties (after
spraying) cannot be obtained even when the requirement that the
.eta..sub.max value .gtoreq.1.times.10.sup.3 mPas is satisfied. For
ensuring that the effects of the present invention (such as
excellent anti-dripping properties (after spraying)) can be
obtained irrespective of the spraying conditions used, it is
preferred that the .eta..sub.max value .gtoreq.5.times.10.sup.5
mPas, and it is more preferred that the .eta..sub.max value
.gtoreq.2.times.10.sup.6 mPas. The viscosity of the spraying
composition may be adjusted depending on the purpose of use of the
spraying composition. In many cases, when the .eta..sub.max value
.gtoreq.5.times.10.sup.5 mPas, the composition used in the present
invention becomes a gel and exhibits no fluidity. From the
viewpoint of stable spraying, it is desired that the .eta..sub.max
value is not more than 1.times.10.sup.9 mPas.
The composition used in the present invention may contain at least
one functional additive in accordance with the purpose of use of
the composition. In the present invention, the term "functional
additive" is used as a generic name for compounds which can have
any contribution to the purpose of use of the spraying composition
in the present invention. Representative examples of functional
additives include an oil compound, a humectant, a surfactant, a
metal oxide, an ultraviolet screener, an inorganic salt, a metal
powder, a gum, a dye, a pigment, a silica compound, a latex, a
water-soluble polymer, an amino acid, a cosmetic ingredient, a
pharmaceutical, an insecticide, a deodorizer, an antimicrobial
agent, an antiseptic agent and a perfume. These are used
individually or in combination. It is important that the
composition containing the functional additive be homogeneous and
that the functional additive does not spoil the effects of the
spraying composition used in the present invention.
For example, in the case where water is used as the liquid
dispersion medium of the composition used in the present invention,
when an oil compound (such as liquid paraffin) is used as a
cosmetic coating oil (functional additive), the cellulose content
is chosen so that a homogeneous O/W emulsion is formed. For
example, when liquid paraffin and water are used in a (liquid
paraffin/water) weight ratio of 20/80 (g/g) and the composition is
prepared by a method in which the emulsification is performed using
an ordinary homomixer, it is desired that the cellulose content is
from 0.8 to 2.5% by weight. Needless to say, these requirements
with respect to the formulation of the spraying composition may
vary depending on the type of the oil compound and the ratios of
the components of the spraying composition.
When a metal powder, such as a metal oxide powder (e.g., titanium
oxide powder) or a copper powder, is used as a functional additive,
it is necessary that the combination of the dispersion medium and
the functional additive is chosen so that the solid microparticles
(metal powder) do not exhibit precipitation or aggregation, thereby
achieving uniform dispersion of the solid microparticles.
Hereinafter, specific examples of functional additives which may be
incorporated in the composition used in the present invention are
described.
Examples of oil compounds include animal fats and oils and
vegetable fats and oils, such as jojoba oil, macadamia nut oil,
avocado oil, evening primrose oil, mink oil, rape-seed oil, castor
oil, sunflower oil, corn oil, cacao oil, coconut oil, rice bran
oil, olive oil, almond oil, sesame oil, safflower oil, soybean oil,
camellia oil, persic oil, cotton seed oil, vegetable wax, palm oil,
palm kernel oil, egg yolk oil, lanolin, and squalene; hydrocarbons,
such as synthetic triglyceride, squalane, liquid paraffin,
vaseline, ceresin, microcrystalline wax, and isoparaffin; waxes,
such as carnauba wax, paraffin wax, spermaceti, beeswax, candelilla
wax, and lanolin; higher alcohols, such as cetanol, stearyl
alcohol, lauryl alcohol, cetostearyl alcohol, oleyl alcohol,
behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol,
hexyldecanol, and octyldodecanol; higher fatty acids, such as
lauric acid, myristic acid, palmitic acid, stearic acid, behenic
acid, isostearic acid, oleic acid, linolenic acid, linoleic acid,
oxystearic acid, undecylenic acid, lanolin fatty acid, hard lanolin
fatty acid, and soft lanolin fatty acid; cholesterols and
derivatives thereof, such as cholesteryl-octyldodecyl-behenyl;
esters, such as isopropyl myristate, isopropyl palmitate, isopropyl
stearate, glycerol 2-ethylhexanoate, and butyl stearate; polar
oils, such as diethylene glycol monopropyl ether, polyoxyethylene
polyoxypropylene pentaerythritol ether, polyoxypropylene butyl
ether, and ethyl linoleate; silicones and derivatives thereof, such
as amino-modified silicone, epoxy-modified silicone,
carboxyl-modified silicone, carbinol-modified silicone,
methacryl-modified-silicone, mercapto-modified silicone,
phenol-modified silicone, silicone having a terminal reactive
group, silicone which is modified with hetero-functional groups,
polyether-modified silicone, methylstyryl-modified silicone,
alkyl-modified silicone, higher fatty acid ester-modified silicone,
hydrophilic group-modified silicone, higher alkoxy-modified
silicone, higher fatty acid-containing silicone, and
fluorine-modified silicone; more specifically, silicone resin,
methyl phenyl polysiloxane, methyl polysiloxane,
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexane siloxane, methylcyclopolysiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane,
polyoxyethylene/methylpolysiloxane copolymer,
polyoxypropylene/methylpolysiloxane copolymer,
poly(oxyethylene/oxypropylene)methylpolysiloxane copolymer,
methylhydrogenpolysiloxane,
tetrahydrotetramethyl-cyclotetrasiloxane,
stearoxymethylpolysiloxane, cetoxy-methylpolysiloxane,
methylpolysiloxane emulsion, highly polymeric methylpolysiloxane,
trimethylsiloxy silic acid, crosslinkable methylpolysiloxane, and
crosslinkable methylphenylpolysiloxane. The oil compound is not
limited to these examples.
Examples of humectants include polyhydric alcohols, such as
maltitol, sorbitol, glycerin, propylene glycol, 1,3-butylene
glycol, polyethylene glycol, and glycol; organic acids and salts
thereof, such as sodium pyrrolidonecarboxylate, sodium lactate, and
sodium citrate; hyaluronic acid and salts thereof, such as, sodium
hyaluronate; hydrolysates of yeast and of yeast extract;
fermentation metabolites, such as a yeast culture broth and a
culture broth of lactic acid bacteria; water-soluble proteins, such
as collagen, elastin, keratin, and sericin; peptides and salts
thereof, such as collagen hydrolysate, casein hydrolysate, silk
hydrolysate, and sodium polyaspartate; saccharides, polysaccharides
and derivatives thereof, such as trehalose, xylobiose, maltose,
sucrose, glucose and plant-derived mucilaginous polysaccharides;
glycosaminoglycans and salts thereof, such as water-soluble chitin,
chitosan, pectin, and chondroitin sulfate and salts thereof; amino
acids, such as glycine, serine, threonine, alanine, aspartic acid,
tyrosine, valine, leucine, arginine, glutamine, and proline;
betaines, such as N-trimethylglycine; sugar amino acid compounds,
such as aminocarbonylation products; plant extracts, such as
extracts of aloe and horse chestnut; and nucleic acid-related
substances, such as urea, uric acid, ammonia, lecithin, lanolin,
squalane, squalene, glucosamine, creatinine, DNA, and RNA. The
humectant is not limited to these examples.
Examples of surfactants include nonionic surfactants, such as
propylene glycol fatty acid ester, glycerol fatty acid ester,
polyoxyethylene glycerol fatty acid ester, polyglycerol fatty acid
ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty
acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene
glycol fatty acid ester, polyoxyethylene castor oil,
polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl
ether, polyoxyethylene phytosterol, polyoxyethylene
polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether,
polyoxyethylene lanolin, polyoxyethylene lanolin alcohol,
polyoxyethylene beeswax derivatives, polyoxyethylene alkyl amine,
polyoxyethylene fatty acid amide, polyoxyethylene alkyl phenyl
formaldehyde condensate, and polyoxyethylene alkyl ether phosphoric
acid (phosphate); anionic surfactants, such as alkylsulfuric ester,
polyoxyethylene alkyl sulfuric ester, alkylbenzenesulfonate, and
.alpha.-olefin sulfonate; cationic surfactants, such as
alkyltrimethylammonium chloride, dialkyldimethylammonium chloride,
and benzalkonium chloride; amphoion surfactants, such as
alkyldimethylaminoacetobetaine and
alkylamidodimethylaminoacetobetaine; natural substances having
surface activity, such as lecithin, lanolin, cholesterol, and
saponin; and hypoallergenic surfactants, such as sulfosuccinates
and ethylene oxide/propylene oxide block copolymers. The surfactant
is not limited to these examples.
Examples of metal oxides include titanium dioxide, alumina, zinc
dioxide, colcothar, yellow oxide, and black iron oxide. The metal
oxide is not limited to these examples. From the viewpoint of
achieving good spraying properties of the composition, it is
preferred that the metal oxide is in such a microparticulate form
that it has an average particle diameter of 10 .mu.m or less,
preferably 5 .mu.m or less.
Examples of ultraviolet screeners include paraaminobenzoic acid and
derivatives thereof; methyl-7N-acetylallantoilanylate;
butylmethoxybenzoylmethane; paramethoxycinnamic acid derivatives,
such as di-paramethoxycinnamic acid-mono-2-glyceryl ethyl
hexanoante, and octylcinnamate; salicylic acid derivatives, such as
amyl salicylate; benzophenone derivatives, such as
2,4-dihydroxybenzophenone; dimethoxybenzylidenedioxo-imidazoline
ethylhexylpropionate; acetylated lanolin alcohol (liquid state);
scutellaria root (i.e., oughon) extract; and
trianilino-p-carboethylhexyloxytriazine. The ultraviolet screener
is not limited to these examples.
With respect to the inorganic salt, there is no limitation, and
there can be used any inorganic salt which is soluble in the liquid
dispersion medium. Examples of inorganic salts include sodium
chloride, calcium chloride, magnesium chloride, ammonium sulfate,
and calcium phosphate. However, depending on the amount of an
inorganic salt used, it is possible that the inorganic salt causes
strong aggregation of cellulose. Therefore, the amount of an
inorganic salt is adjusted so as not to cause adverse effects on
the spraying properties of the composition.
With respect to the metal powder, there is no limitation, and there
can be used a powder of any metal, such as gold, silver, copper,
aluminum, magnesium, zinc and iron. However, from the viewpoint of
achieving good spraying properties of the composition, it is
preferred that the metal powder has an average particle diameter of
10 .mu.m or less, preferably 5 .mu.m or less.
Examples of gums include gum arabic, xanthan gum, guar gum, locust
bean gum, quince seed, and carrageenan. The gum is not limited to
these examples.
The dye and pigment can be appropriately selected from those
employed in the various fields, such as fiber coloring, various
types of printing, copying machines, and writing instruments. The
dye and pigment are not limited to those employed in these fields.
There can be used any dye and/or any pigment as long as they have a
coloring ability.
Examples of silica compounds include zeolite, montmorillonite,
asbestos, smectite, mica, fumed silica, colloidal silica, and
nanoporous silica. The silica compound is not limited those
examples. From the view-point of achieving good spraying properties
of the composition, it is preferred that the silica compound is in
such a microparticulate form that it has an average particle
diameter of 10 .mu.m or less, preferably 5 .mu.m or less.
Examples of latexes include a styrene-butadiene copolymer latex and
an acrylic polymer latex. There can be used any polymer latex which
is obtained by an emulsion polymerization.
Examples of water-soluble polymers include polyethylene glycol,
polyvinyl alcohol, cationized cellulose, carboxyvinyl polymer,
polyvinyl pyrrolidone, a polyvinyl pyrrolidone/vinyl acetate
copolymer, polyacrylic acid, polyacrylamide, alginic acid,
polydextrose, carboxymethyl cellulose, and hydroxyethyl cellulose.
The water-soluble polymer is not limited to these examples.
With respect to the amino acid, any known amino acid (such as
glutamic acid, aspartic acid, glycine and lysine) can be used.
Examples of cosmetic ingredients include arbutin, kojic acid,
ascorbic acid and derivatives thereof, such as
magnesium-L-ascorbyl-2-phosphate, glutathione, glycyrrhiza extract,
clove extract, tea extract, astaxanthin, bovine placenta extract,
tocopherol and derivatives thereof, tranexamic acid and salts
thereof, azulene, whitening elements, such as
.gamma.-hydroxybutyric acid; organic acids, such as citric acid,
malic acid, tartaric acid, lactic acid, adipic acid, glutamic acid,
aspartic acid, and maleic acid; B vitamins, such as vitamin B6
hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, and
vitamin B2 and derivatives thereof; C vitamins, such as ascorbic
acid, ascorbic acid sulfate, and ascorbic acid phosphate; E
vitamins, such as .alpha.-tocopherol, .beta.-tocopherol, and
.gamma.-tocopherol; D vitamins; other vitamins, such as vitamin H
and pantothenic acid; blood circulation stimulators, such as
nicotinic acid amide, benzyl nicotinate, .gamma.-oryzanol,
allantoin, glycyrrhizic acid (salt), glycyrrhetic acid and
derivatives thereof, hinokitiol, bisabolol, eucalyptol, thymol,
inositol, saponins, (e.g., quillaia saponin, azuki-bean saponin and
sponge gourd saponin), tranexamic acid, pantothenylethyl ether,
ethynylestradiol, placenta extract, sialid extract, cepharanthine,
and vitamin E and derivatives thereof; local stimulators, such as
capsicum tincture, ginger tincture, cantharis tincture, and benzyl
nicotinate; anti-inflammatory agents, such as glycyrrhetic acid,
glycyrrhizic acid derivatives, allantoin, azulene, aminocaproic
acid, and hydrocortisone; astringents, such as zinc oxide, zinc
sulfate, allantoin hydroxyaluminum, aluminum chloride, zinc
sulfophenolate, and tannic acid; algefacients (refreshing agents),
such as menthol and camphor; antihistamine agents;
silicon-containing compounds, such as polymeric silicone and cyclic
silicone; various pharmaceuticals, such as antioxidants, e.g.,
tocopherols and gallic acid; and extracts of natural products, such
as plants, animals, bacteria and a part of a natural product,
wherein the extracts are obtained by extraction using a solvent
(such as, an organic solvent, an alcohol, a polyhydric alcohol,
water, or a water-soluble alcohol) or by hydrolysis. Examples of
such natural products include yeast (such as, saccharomyces),
filamentous fungi, bacteria, bovine placenta, human placenta, human
umbilical cord, wheat grains, soybeans, bovine blood, swine blood,
cockscomb, chamomile, cucumber, rice, shea butter, white birch,
tea, tomato, garlic, witch hazel (i.e., hamamelis), rose, sponge
gourd, hop, peach, apricot, lemon, kiwi fruit, dokudami (i.e.,
Hottuynia cordata), capsicum, Sophora flavescens, sorrel, nuphar
rhizome (i.e., spatterdock), sage, yarrow, mallow, cnidium rhizome,
sialid, thyme, Japanese angelica root, spruce, birch, field
horsetail, horse chestnut tree, strawberry geranium, arnica, lily,
mugwort, peony, aloe, aloe vera, scutellaria root (i.e., oughon),
cork tree, silk tree, safflower, gardenia fruit, lithospermum root,
jujube fruit, dried orange peel, ginseng, coix seed, adlay,
gardenia, and sawara cypress. The cosmetic ingredient is not
limited to those examples.
With respect to the pharmaceutical, there is no limitation, and
there can be used any pharmaceutical (inclusive of traditional
Chinese medicines) which exhibits a medicinal effect. However, the
efficacy of a pharmaceutical greatly varies depending on a compound
which coexists with the pharmaceutical. Therefore, the formulation
of the composition should be appropriately chosen so that the
pharmaceutical can exhibit a satisfactory efficacy.
Representative examples of insecticides include camphor,
naphthalene, paradichlorobenzene, paraformaldehyde, chloropicrin,
pyrethrum, sulfonbenzaldehyde, and a phenylmethane compound. The
insecticide is not limited to these examples.
With respect to the deodorizer, there is no limitation, and there
can be used any compound which exhibits a deodorizing effect. The
deodorizer may or may not be solid and may or may not be
dissolvable. When the deodorizer is solid, from the viewpoint of
achieving good spraying properties of the composition, it is
preferred that the deodorizer is in such a microparticulate form as
have an average particle diameter of 10 .mu.m or less, preferably 5
.mu.m or less.
Examples of antimicrobial agents and antiseptic agents include
benzoic acid and salts thereof, salicylic acid and salts thereof,
sorbic acid and salts thereof, alkyl parahydroxybenzoate (e.g.,
ethylparaben or butylparaben) and salts thereof, dehydroacetic acid
and salts thereof, parachlorometacresol, hexachlorophene, boric
acid, resorcin, tribromosalan, orthophenylphenol, chlorhexidine
gluconate, thiram, photosensitizing dye No. 201, phenoxyethanol,
benzalkonium chloride, benzethonium chloride, halocarban,
chlorhexidine chloride, trichlorocarbanilide, tocopherol acetate,
zinc pyrithione, hi-nokitiol, phenol, isopropyl methylphenol,
2,4,4-trichloro-2-hydroxyphenol, and hexachlorophene. The
antimicrobial agent and antiseptic agent are not limited to these
examples.
With respect to the perfume, there is no limitation, and there can
be used any material which serves as a perfume. It is preferred
that the formulation of the composition is appropriately chosen so
that the adverse effects, if any, of other components on the scent
of the perfume are as small as possible.
With respect to the ionic compound as a functional additive, an
explanation is made below. It is preferred that, in the
composition, the content of the functional additive other than the
ionic compound is from 0.1 to 60% by weight, more advantageously
from 0.1 to 40% by weight, still more advantageously from 0.2 to
30% by weight.
The functional additive is not limited to these. Any other
functional additives which are appropriately selected may be
incorporated into the composition, depending on the purpose of use
of the composition. The functional additives are used individually
or in combination. In selecting a functional additive, it is
especially important that the composition containing the functional
additive selected have a good homogeneity such that no grainy
feeling or no phase separation is exhibited. Also, it is especially
important that the composition containing the functional additive
selected exhibit almost no stringiness.
The spraying composition used in the present invention is a
microparticle dispersion. In this respect, the composition used in
the present invention is a colloid. However, the composition used
in the present invention has a unique property that it can form a
transparent, highly stable gel. This means that the spraying
composition used in the present invention is a very unique colloid
which has conventionally not been reported. The reason for the
presence of such unique property of the spraying composition used
in the present invention resides in that particulate cellulose
(which is the main component) has the high ability to form hydrogen
bonds therebetween. As only other transparent gels having a similar
property, there can be mentioned an aqueous dispersion of fumed
silica and an aqueous dispersion of hydrophilic smectite. However,
these conventional dispersions pose problems in that, when an
organic solvent is added, aggregation is likely to occur and that
the coating forming abilities of these dispersions are extremely
poor. Therefore, with respect to the practical usefulness, the
composition used in the present invention is distinct from these
conventional dispersions. It is known that, in general, when an
ionic compound is added to a colloidal dispersion, the colloidal
dispersion undergoes aggregation. Specifically, in the case of a
certain type of colloidal dispersion, when an ionic compound, such
as an inorganic salt having the strong ability to induce
aggregation (e.g., a trivalent inorganic salt, such as ammonium
chloride), is added to the dispersion, aggregation occurs even when
the amount of the ionic compound is as small as only 0.1% by
weight, thus adversely affecting the stability or the like of the
resultant composition. By contrast, the present inventors have
found that, when an ionic compound as a functional additive is
added to the composition used in the present invention under
specific conditions, a stable composition can be provided.
That is, the present inventors have found the following. When a
functional additive is added to the spraying composition used in
the present invention, the stability of the resultant
additive-containing composition may vary depending on the type of
the additive used, the type of the dispersion medium used, the
cellulose content and the like. However, even in the case of the
use of an ionic compound as a functional additive, when the content
of the ionic compound (as a functional additive) in the composition
is from 0.1 to 10% by weight, the composition can maintain a high
stability. The content of the ionic compound in the composition is
preferably in the range of from 0.1 to 5% by weight, more
preferably from 0.2 to 3% by weight. When the content of the ionic
compound is less than 0.1% by weight, the ionic compound is
generally incapable of performing a satisfactory function as a
functional additive. On the other hand, when the content of the
ionic compound is more than 10% by weight, the stability of the
composition becomes lowered.
In the present invention, the term "ionic compound" is used as a
generic name for compounds which are capable of being dissolved as
an ion in the dispersion medium. Examples of ionic compounds
include amphoteric compounds, cationic compounds and anionic
compounds. The cellulose, optional functional microparticles and
the like which are contained in the composition used in the present
invention may induce colloidal properties in the composition.
Therefore, when the ionic compound is added to the composition, the
formulation of the composition is adjusted so that the content of
the ionic compound is in the above-mentioned range and that the
stability of the components of the composition is maintained at a
high level (this means a state in which, when the composition is
visually observed, the composition is homogeneous and exhibits no
phase separation of the components with the lapse of time).
The type of the ionic compound is especially important for choosing
the formulation of the composition. Use of an amphoteric compound
or a cationic compound is especially preferred because these ionic
compounds can be widely used with only a relatively small
limitation as long as the amount of the ionic compound is in the
above-mentioned range.
The term "amphoteric compound" used herein means a compound which
has both a positive ionic group and a negative ionic group in one
molecule and which is electrically neutral in such a state as
dissolved in the dispersion medium. Examples of amphoteric
compounds include various amino acids and salts thereof and
betaines. Examples of cationic compounds include cationic
surfactants (such as alkyltrimethylammonium chloride and
dialkyldimethylammonium chloride), water-soluble cationic polymers
(such as cationized cellulose) and low molecular weight cationic
molecules, such as lysine and lysine salts. Examples of anionic
compounds include anionic surfactants (such as alkyl sulfate esters
and polyoxyethylene alkyl sulfate esters), water-soluble anionic
polymers (such as polyacrylic acid and carboxymethyl cellulose),
and water-soluble low molecular weight organic compounds, such as
glutamic acid, a glutamate, citric acid and a citrate, which are
functional additives capable of functioning as an anion or existing
in the form of an anion in the composition. Further examples of
ionic compounds include inorganic salts which are soluble in the
dispersion medium, such as sodium chloride, magnesium chloride,
calcium chloride, sodium hydrogencarbonate, sodium carbonate,
ammonium sulfate, potassium phosphate and ammonium nitrate. There
can also be mentioned inorganic acids, such as sulfuric acid,
hydrochloric acid and phosphoric acid, and other inorganic
compounds, such as sodium hydroxide and potassium hydroxide.
Stringing is a phenomenon which is caused by the presence of a high
molecular weight polymer component dissolved in the liquid
dispersion medium. Therefore, for example, when a water-soluble
polymer is dissolved in the aqueous dispersion medium, the
molecular weight and amount of the polymer should be appropriately
selected so as to prevent the occurrence of stringing.
The spraying composition used in the present invention has high
thixotropy and, thus, when this composition is sprayed, the
viscosity of the composition is lowered to thereby form an
excellent spray or foam, but the original viscosity of the
composition is quickly recovered before the sprayed fine particles
of the composition attach to a surface to be coated. Therefore,
dripping is very unlikely to occur after the sprayed composition
attaches to a surface to be coated. Further, the spraying
composition used in the present invention exhibits the following
excellent properties. The composition exhibits an excellent thermal
stability such that the viscosity of the composition is not lowered
even at a high temperature of 50.degree. C. or more. The
composition is free from tackiness which is characteristic of a
water-soluble polymer. The composition exhibits excellent
spreadability after coating. The composition exhibits high
dispersion stability and is capable of forming a strong coating,
thereby enabling the formation of a strong coating having
immobilized thereon a functional compound. At the same time, with
respect to the fixation of the fine particles of the sprayed
composition to the surface coated, such as skin and a substrate,
the spraying composition used in the present invention is largely
improved by virtue of the amphiphilic properties and viscosity
increasing effects of cellulose, as compared to the case of the
liquid dispersion medium used solely.
In addition, since cellulose (having a high safety) is used as a
viscosity modifier for the spraying composition used in the present
invention, the composition is advantageous in that, when components
having a high safety are selected as the additional components for
the composition, it is easy to design the formulation of the
composition so as to, for example, minimize the occurrence of
irritation even after the drying of the liquid dispersion medium of
the composition which has been applied to the human body (such as
skin). That is, it is possible to provide a spraying composition
having a very high safety.
Further, the composition used in the present invention can be
produced so as to have high transparency, when an appropriate type
of cellulose and an appropriate formulation are selected. Herein,
the term "high transparency" means that, when the composition is
diluted with water to have a particulate cellulose concentration of
0.05% by weight, the resultant aqueous composition exhibits a
transmittance of 80% or more, preferably 90% or more, to visible
rays having a wavelength of 660 nm.
Further, the composition of the present invention
When the composition which is produced so as to have high
transparency is sprayed, the resultant spray coating layer
maintains its transparency even after drying. Therefore, such a
spraying composition can be used advantageously in fields where
high transparency and high smoothness are required for the spray
coating layer. For preparing a composition which can form a spray
coating layer having a satisfactory level of transparency and
smoothness, it is important to prevent not only cellulose but also
components other than cellulose from undergoing aggregation. This
is because the transparency of the composition is markedly lowered
by aggregation. Further, for the purpose of obtaining high
transparency, it is necessary to limit the content of the ionic
compound to a value within the above-mentioned range.
For example, for adding a surfactant to the composition without
lowering the transparency thereof, it is effective to add a
nonionic surfactant or an amphoteric surfactant, such as
betaine.
Further, as mentioned above, when a water-soluble polymer is added
as a dispersion stabilizer for the dispersed components (such as a
pigment), it is important that the polymer be added in a limited
amount which does not cause stringing, thereby maintaining the
spraying properties of the composition. From the viewpoint of
improving the transparency of the composition, polymeric
electrolytes (ionic compounds), such as polyacrylic acid, alginic
acid and carboxymethyl cellulose, are disadvantageous because they
tend to promote the aggregation of cellulose and lower the
transparency of the spraying composition. Therefore, it is desired
that the amount of the polymeric electrolyte is lowered to a level
which causes no adverse effects on the transparency of the spraying
composition. Alternatively, it is desired that a nonionic compound,
such as polyethylene glycol or polyvinyl alcohol, or a mixture of a
nonionic water-soluble polymer and a polymeric electrolyte is used
as a dispersion stabilizer.
With respect to the above-mentioned evaluation of the transmittance
of the spraying composition, the preparation of the aqueous
composition (particulate cellulose concentration: 0.05% by weight)
and the measurement of the transmittance were performed as
follows.
Ion exchanged water was added to the spraying composition so as to
adjust the cellulose concentration thereof to 0.05% by weight.
Next, the resultant mixture was subjected to a treatment for
dispersing, at 15,000 rpm for 10 minutes by means of a homogenizer
(T.K. Lobo. mics.TM., manufactured and sold by TOKUSHU KIKA KOGYO
CO., Ltd., Japan), thereby obtaining a homogenized aqueous
composition. The transmittance of the aqueous composition was
measured as follows. The aqueous composition was placed in a quartz
cell (light path: 1 cm), and measurement was performed using a
UV-visual range spectrophotometer (UV-Vis spectrophotometer
UV-2500PC, manufactured and sold by SHIMADZU Corporation, Japan).
The transmittance was defined as a I.sub.t/I.sub.0 ratio (in terms
of a percentage (%)), wherein I.sub.t represents the transmittance
intensity (=transmittance intensity of the aqueous composition),
and I.sub.0 represents the incident light intensity of visible rays
having a wavelength of 660 nm (approximated by the transmittance
intensity of light having passed through ion exchanged water (as a
reference sample) placed in the same cell).
Next, the method for preparing the composition for use in the
present invention is explained in detail.
As explained below, in the preparation of the spraying composition
for use in the present invention, first, cellulose is dispersed in
a liquid dispersion medium to thereby obtain a cellulose dispersion
as a raw material (for the general purpose, the cellulose
dispersion is a cellulose/water dispersion). Then, in accordance
with the purpose of use of the spraying composition, a further
operation is performed in which various additives are added to the
cellulose dispersion, followed by stirring, and/or the cellulose
dispersion is diluted with a liquid dispersion medium, followed by
stirring, to thereby obtain a spraying composition.
As an example of a cellulose dispersion which can be advantageously
used as a raw material for producing the composition for use in the
present invention, there can be mentioned a crystalline cellulose
dispersion described in Unexamined Japanese Patent Application
Laid-Open Specification No. Hei 3-163135.
A dispersion of cellulose having low crystallinity can be obtained
by the method described in WO99/28350. When such a dispersion of
low crystallinity cellulose is used as a raw material for producing
the spraying composition for use in the present invention, there is
an advantage in that a spraying composition which is a gel and has
high transparency can be obtained under certain conditions.
Hereinbelow, a detailed explanation is made on the case where this
cellulose dispersion is used as a raw material for producing the
spraying composition. In this case, first, a natural or regenerated
cellulose material is dissolved in an aqueous inorganic acid
solution, such as sulfuric acid, and then, the cellulose material
in the resultant solution is reprecipitated by using a precipitant,
such as water, followed by hydrolysis under heating. The resultant
hydrolysis reaction mixture is washed and concentrated to thereby
remove the inorganic acid and obtain an aqueous cellulose
dispersion. If desired, the dispersion medium may be replaced with
an organic solvent, and the resultant dispersion may be subjected
to a homogenization treatment by means of a mixer.
As mentioned above, the liquid dispersion medium contained in the
cellulose dispersion is generally water. However, in accordance
with the purpose of use of the spraying composition, a part or
whole of the liquid dispersion medium may be replaced with a
water-soluble organic solvent (such as methanol, ethanol,
isopropanol, acetone, acetonitrile, dimethyl sulfoxide,
dimethylformamide or dimethylacetamide), or by a mixture of these
water-soluble organic solvents.
When a water-soluble organic solvent is used as the dispersion
medium for preparing the cellulose dispersion, as explained above
in detail in connection with the composition for use in the present
invention, the water-soluble organic solvent is used in an amount
of from 1 to 90% by weight, preferably from 3 to 60% by weight,
more preferably from 5 to 50% by weight, based on the weight of the
dispersion. When the amount of the water-soluble organic solvent is
less than 1% by weight, any great effect cannot be obtained by the
replacement of water with the water-soluble organic solvent. On the
other hand, since the replacement of water which binds to the
particulate cellulose is technically difficult, addition of the
water-soluble organic solvent in an amount of more than 90% by
weight is substantially impossible.
In special cases where it is desired to prepare a spraying
composition containing a nonaqueous, strongly hydrophobic
dispersion medium, it is necessary to use a hydrophobic organic
solvent, such as a hydrocarbon (e.g., hexane or toluene) or an
ester (e.g., ethyl acetate). In this case, after the removal of the
inorganic acid from the above-mentioned hydrolysis reaction
mixture, the water present in the resultant aqueous cellulose
dispersion is replaced with a water-soluble organic solvent and,
then, the water-soluble organic solvent is, in turn, replaced with
a hydrophobic organic solvent. Alternatively, a water-non-soluble
hydrophobic organic solvent is added to the aqueous cellulose
dispersion, and the resultant mixture is subjected to a treatment
for emulsification/dispersion (preliminary emulsification).
The thus-obtained cellulose dispersion as such can be used as the
spraying composition for use in the present invention. Instead, the
thus obtained cellulose dispersion may be used as a precursor for
producing a spraying composition (of the present invention) which
is adapted to a specific use; the use as a precursor can be made
by, for example, any of the following methods:
a method (process A) in which an additional liquid dispersion
medium and a functional additive are added, in an appropriate
order, to the cellulose dispersion (as a precursor) to thereby
obtain a composition, followed by a treatment for dispersing the
components of the composition;
a method (process B) in which the cellulose dispersion (as a
precursor) is subjected to the below-mentioned treatment for high
degree pulverization, and then an additional liquid dispersion
medium and a functional additive are added thereto in an
appropriate order to thereby obtain a composition, followed by a
treatment for dispersing the components of the composition; and
a method (process C) in which an additional liquid dispersion
medium and a functional additive are added, in an appropriate
order, to the cellulose dispersion (as a precursor) to thereby
obtain a composition, and then the composition is subjected to a
preliminary treatment for dispersing the components of the
composition to obtain a preliminary dispersion, followed by the
below-mentioned treatment for high degree pulverization.
The method of using the cellulose dispersion as a precursor for
preparing the spraying composition is not limited to these
processes A to C. The method of using the cellulose dispersion as a
precursor for preparing the spraying composition is not
particularly limited as long as the cellulose dispersion as a
precursor can be well mixed with an additional liquid dispersion
medium and a functional additive, thereby obtaining a homogeneous
composition.
In the case of the processes B and C mentioned above, by virtue of
the operation that the precursor or the preliminary dispersion is
subjected to the treatment for high degree pulverization by means
of, for example, a high pressure/super high pressure homogenizer or
the like, there can be obtained a more advantageous spraying
composition. As an apparatus for performing the treatment for high
degree pulverization, there can be mentioned, for example,
Microfluidizer.TM. (manufactured and sold by Mizuho Kogyo Kabushiki
Kaisha, Japan), Ultimaizer.TM. (manufactured and sold by Sugino
Machine Limited, Japan) and Nanomizer.TM. (manufactured and sold by
Yoshida Kikai Co., Ltd., Japan). For example, by using the process
B (in which the precursor is subjected to the treatment for high
degree pulverization), a composition for use in the present
invention having more improved transparency can be obtained. On the
other hand, by using the process C (in which the preliminary
dispersion is subjected to the treatment for high degree
pulverization), there can be obtained an emulsion containing oil
globules having a very small size of a submicron level (or water
globules having a very small size of a submicron level, depending
on the production conditions). In many cases, such an emulsion is
white opaque. The treatment for high degree pulverization may be
conducted two or more times.
For the treatment for dispersing conducted in the processes A and B
and for the preliminary treatment for dispersing conducted in the
process C, various machines conventionally used for treatments for
mixing and/or dispersing can be used. Specifically, there can be
used kneading machines, such as a vacuum homomixer, a disperser, a
propeller mixer and a kneader; various grinders; a blender; a
homogenizer; an ultrasonic emulsifier; an colloid mill; a pebble
mill; a ball mill; a planetary ball mill; a bead mill and a high
pressure homogenizer.
An appropriate treatment for mixing and/or dispersing can be
selected in accordance with the purpose of use of the spraying
composition and the formulation of the spraying composition. The
operation conditions for preparing the composition (such as the
temperature, the conditions for dispersing, and the order of adding
the additives) are appropriately selected in accordance with the
formulation of the composition. For example, when two or more
functional additives are used in combination, it may be effective
to introduce the functional additives by a method in which,
depending on the solubility and precipitation properties of the
additives, the additives are preliminarily dissolved in a liquid
dispersion medium to obtain a solution and, then, the obtained
solution is added to the composition. The composition used in the
present invention has a characteristic that it is a viscous
composition, irrespective of whether it is a highly transparent
composition or an opaque composition (such as an emulsion or a
pigment dispersion). Therefore, in many cases, the composition used
in the present invention (obtained by the above-mentioned treatment
for dispersing) is likely to contain many bubbles. In such case, it
is effective to conduct a vacuum deaeration treatment at the end of
the production process or add an antifoaming agent, such as
ethanol, to the composition.
The pH value of the composition is in the range of from 2.0 to
11.0, preferably from 3.0 to 10.0, more preferably from 3.5 to 9.5.
When the pH value of the composition is in the above-mentioned
range, a highly homogenous spraying composition having excellent
stability can be obtained. On the other hand, when the pH value of
the composition is less than 2.0 or greater than 11.0, cellulose,
which is an essential component of the composition, is likely to
aggregate and cause adverse effects on the homogeneity and
stability of the composition. The pH value of the composition for
use in the present invention can be controlled so as to fall within
the above-mentioned range by appropriately adding to the
composition an inorganic acid, an inorganic salt, an organic acid
or an organic salt.
Hereinbelow, an explanation is made on the method for producing a
spraying composition which contains an oil component or a mixture
of two or more oil components as an additive, i.e., a spraying
composition in the form of an oil-in-water emulsion (hereinafter,
frequently referred to as an "O/W emulsion").
With respect to the cellulose used in the present invention, the
cellulose itself is emulsifiable and, thus, an emulsion can be
prepared without using a surfactant. When a surfactant is used as
an emulsifier, cellulose functions as an emulsion stabilizer.
An emulsion can be prepared in accordance with a conventional
method for preparing an O/W emulsion.
For example, an emulsion can be prepared as follows. An aqueous
dispersion of low crystallinity particulate cellulose is prepared
in the above-mentioned manner. An oil component or a mixture of two
or more oil components is mixed with the aqueous cellulose
dispersion at 70 to 80.degree. C., and the resultant mixture is
emulsified. The emulsification can be conducted by means of a
conventional emulsifier or an apparatus which is capable of
effecting a more powerful emulsification, such as a high pressure
homogenizer or a super high pressure homogenizer. Thus, the
composition for use in the present invention is obtained which is
an emulsion containing an oil component or a mixture of two or more
oil components as an additive.
By the above-mentioned method, an emulsion can be obtained without
using any surfactant. When a surfactant is used which is a
conventional emulsifier and, also, low crystallinity particulate
cellulose is used as an auxiliary emulsifier (emulsion stabilizer),
an emulsion can also be prepared in the similar manner.
Further, a stable emulsion in the form of a gel can be obtained by
a method in which an aqueous gel containing cellulose, and an O/W
emulsion containing no cellulose, are separately prepared and,
then, the gel and the emulsion are mixed together.
The cellulose-containing composition for use in the present
invention which is produced by the above-mentioned method is either
a transparent dispersion or a translucent or opaque dispersion.
When the composition is a transparent dispersion containing almost
no foamable surfactant, such as a non-ionic surfactant (which does
not lower the transparency of the composition), such a composition
can produce excellent mist. On the other hand, when the composition
contains at least a predetermined amount of a foamable surfactant,
such as a nonionic surfactant (which does not lower the
transparency of the composition), such a composition can function
as a special embodiment of the present invention, namely a
so-called foaming composition which produces a foam when the
composition is extruded from a spray container device. In this
case, due to the network formed by the particulate cellulose
contained in the foam, the foam exhibits very high stability,
thereby exhibiting the excellent effects of the present invention
as a foamable spraying composition.
With respect to the translucent or opaque dispersion, it is
considered that a dispersion becomes translucent or opaque when,
for example, one of the following cases applies: a case where
cellulose contained in the dispersion has a particle diameter on
the micrometer order; a case where cellulose forms a loose
aggregation; a case where an O/W emulsion is formed by an oil
compound used as one of the components; a case where the dispersion
contains a microparticulate component which is insoluble in the
dispersion medium and which has a particle size which induces light
scattering; and a case where the dispersion contains at least a
predetermined amount of a foamable ionic surfactant (in this case,
loss of transparency of the composition is caused by the loose
aggregation of cellulose). Except for the case where the
composition is a dispersion containing a foamable ionic surfactant
in at least a predetermined amount, the composition in any case can
produce excellent mist. When the composition is a dispersion
containing a foamable ionic surfactant in at least a predetermined
amount, the composition can function advantageously as a foamable
spraying composition.
In the present invention, the above-mentioned composition is packed
in a spray container device to obtain a spray pack.
With respect to the spray container device used in the present
invention, there is no particular limitation. Any spray container
device can be used as long as the device is capable of being easily
packed with the composition and spraying the composition, and the
packed composition is capable of functioning as a spraying
composition. However, from the viewpoint of the general-purpose
properties and the high accuracy of spraying, the following three
types of spray container devices are especially preferred.
One of the preferred spray container devices used in the present
invention is a dispenser type spray container device equipped with
a pump type nozzle which is capable of spraying under conditions
wherein the internal pressure of the container is maintained at
atmospheric pressure. Such a spray container device is capable of
forming mist under atmospheric pressure without using a pressurized
gas or the like. Further, this container device has a relatively
simple structure and has high safety and high portability. This
spray container device is composed of a screw type container which
is for accommodating the composition packed therein and which has,
fitted at its inlet, an extrusion pump type nozzle equipped with a
suction tube placed inside of the container. The term "dispenser
type spray container device" used herein is intended to cover all
such devices inclusive of improved devices having a pump type
nozzle which is modified for improving the spraying performance
thereof. The spraying performance of a spray container device
varies depending on the hole diameter of the spraying nozzle and
the extrusion volume of the pump, and these conditions are selected
in accordance with the purpose of use of the spray pack.
Since the average particle diameter of the cellulose which is
contained in the composition packed in the spray container device
is 10 .mu.m or less, in general, clogging of the nozzle hole is
unlikely to occur under the conditions for using the spray
container device (i.e., the inner diameter of the nozzle is about
50 to 1,000 .mu.m), and therefore the spraying (or foaming) can be
performed without any problems. In addition, since the composition
used in the present invention has a property such that the
viscosity thereof is lowered when only a very small amount of
stress is applied, drawing up of the composition through the
suction tube can be performed satisfactorily when the inner
diameter of the suction tube is about 0.1 mm or more.
The above-mentioned conditions with respect to the nozzle and the
suction tube also apply to the below-mentioned other two types of
spray container devices.
A trigger type spray container device is also preferred in the
present invention. A trigger type spray container device is
suitable for the spraying of household detergents, textile
starches, kitchen detergents and the like, and it is composed of a
container which is for accommodating the composition packed therein
and which has, fitted at its inlet, a pistol-shaped, trigger type
spray device. Like the dispenser type spray container device, this
spray container device is capable of spraying under conditions
wherein the internal pressure of the container is maintained at
atmospheric pressure, and this spray container device has high
general-purpose properties for the spraying of a liquid. The term
"trigger type spray container device" used herein is intended to
cover all such devices inclusive of improved devices which are
modified for improving the spraying performance thereof. As
mentioned above, the spraying composition used in the present
invention is a highly viscous composition which may be in the form
of a gel. Irrespective of whether or not the composition is a gel,
the composition used in the present invention is advantageous in
that, as in the case of the dispenser type spray container device,
by the use of a spray pack obtained by packing the composition used
in the present invention into a trigger type spray container
device, excellent spray (or foam) can be produced under any
operation conditions.
In addition, an aerosol spray container device can be mentioned as
another example of a preferred spray container device used in the
present invention. In the case of the use of an aerosol spray
container device, an aerosol propellant is packed in the container
together with the spraying composition. By virtue of the use of the
aerosol propellant, an aerosol spray container device enables
continuous spraying or continuous formation of foam, which cannot
be realized by the above-mentioned two types of devices. The term
"aerosol spray container device" used herein is intended to cover
all such devices inclusive of improved devices which are modified
for improving the spraying performance thereof. Use of an aerosol
spray container device is preferred especially when the spraying
composition used in the present invention is used as a foaming
composition. In general, the use of an aerosol spray container
device enables the formation of a finer spray than in the case of
the use of the above-mentioned other two types of spray container
devices, which are operated under conditions wherein the internal
pressure of the container is maintained at atmospheric pressure.
Examples of aerosol propellants used in the present invention
include dimethyl ether, liquefied petroleum gas, carbon dioxide
gas, nitrogen gas, argon gas, air, oxygen gas and flon gas
(chlorofluorocarbon gas). However, the aerosol propellant is not
limited to these gases. These gases can be used individually or in
combination. The aerosol propellant is selected taking into
consideration various factors, and one of the criteria for
selecting the aerosol propellant is the solubility of the aerosol
propellant in the liquid dispersion medium of the spraying
composition. For example, when a large part of the dispersion
medium is a strongly hydrophobic organic solvent (such as
isopropanol or n-hexane), a liquefied petroleum gas is preferred as
an aerosol propellant. When the water content of the spraying
composition is high, dimethyl ether is preferred as an aerosol
propellant.
With respect to the use of any spray container device, the
cellulose-containing composition used in the present invention is
advantageous in that, when the composition is formulated so as to
exhibit a high viscosity enough to take a gel form, to thereby
prevent the composition from flowing in the inside of the
container, the spraying (or formation of foam) can be performed in
any direction. In an extreme case, such a spray pack of the present
invention can be used even when the spray pack is held upside
down.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinbelow, the present invention will be described in more detail
with reference to the following Examples and Comparative Examples,
but they should not be construed as limiting the scope of the
present invention.
First, an explanation is made with respect to the methods for
evaluating the compositions prepared in the Examples and the
Comparative Examples.
The structural parameters and the properties were evaluated by the
following methods.
(1) Characterization of Cellulose in a Composition
{circle around (1)} The measurement of a wide-angle X-ray
diffraction pattern was performed using an X-ray diffraction
apparatus (RU-300, a lint system is attached thereto; manufactured
and sold by Rigaku Corporation, Japan), and then x.sub.I and
x.sub.II were determined by the above-mentioned method. {circle
around (2)} The average particle diameter of particulate cellulose
was determined by the above-mentioned method using the Laser
Diffraction/Scattering Type Particle Size Measuring Apparatus
LA-920 (manufactured and sold by HORIBA Ltd., Japan). {circle
around (3)} The average degree of polymerization (DP) was evaluated
by the following method. A dried cellulose sample was dissolved in
cadoxene to obtain a diluted cellulose solution. The specific
viscosity of the diluted cellulose solution was measured at
25.degree. C. using an Ubbellohde viscometer. From the specific
viscosity, an intrinsic viscosity value [.eta.] was obtained. From
the intrinsic viscosity value [.eta.], a weight average degree of
polymerization (DP) was calculated. (2) Viscosity of a Composition
(.eta..sub.max)
The viscosity (.eta..sub.max) was measured using a cone-plate type
rotating viscometer (RS-100, manufactured and sold by Haake
Company, German) under conditions wherein cone angle: 4.degree.;
plate diameter: 35 mm; the shear rate (.gamma.') region: from
1.times.10.sup.-3 s.sup.-1 to 1.times.10.sup.2 s.sup.-1, and the
measuring temperature: 25.degree. C.
(3) Relative Transmittance of a Diluted Composition to Visible Rays
Having a Wavelength of 660 nm
A composition was diluted with water to have a particulate
cellulose concentration of 0.05% by weight (wherein, when a
viscosity modifier other than cellulose was employed, the
concentration of the viscosity modifier employed was adjusted to
0.05% by weight). The resultant aqueous composition was subjected
to a treatment for dispersing, at a revolution rate of 15,000 rpm
for 10 minutes by means of a homomixer (T. K. ROBO MICS.TM.,
manufactured and sold by TOKUSHU KIKA KOGYO Co., Ltd., Japan), to
thereby obtain a diluted aqueous composition. The relative
transmittance of the diluted aqueous composition was measured by
means of a UV-visual range spectrophotometer (UV-2500PC,
manufactured and sold by SHIMADZU Corporation, Japan).
(4) Evaluation of the Spraying Properties
With respect to the spraying properties of various spraying
compositions, the following evaluations were performed. {circle
around (1)} State of spray; a spraying was performed and the state
of the spray was evaluated in accordance with the following
criteria.
The spraying composition cannot be shot from the nozzle, that is, a
spraying cannot be performed. .fwdarw.X
Although the spraying composition can be shot from the nozzle, the
spraying composition cannot form a mist. .fwdarw..DELTA.
The spraying composition can be shot from the nozzle and form an
excellent mist. .fwdarw..largecircle. {circle around (2)}
unevenness in spray coating; A frosted glass plate having a size of
18 cm.times.18 cm was vertically disposed. A spraying was performed
once toward the glass plate, from a position which was at a
horizontal distance of 20 cm from the frosted glass plate, and the
distribution of droplets which attached to the surface of the
frosted glass plate was observed immediately after the spraying.
The unevenness in the spray coating was evaluated in accordance
with the below-mentioned criteria, as compared to the results of a
spraying which was performed in the same manner as mentioned above
except that ion-exchanged water was used instead of the spraying
composition.
The spray coating on the frosted glass plate is interspersed with
large droplets and, thus, a marked unevenness in the spray coating
is observed. .fwdarw.X
Although the spray coating on the frosted glass plate is not
interspersed with large droplets, the distribution of the droplets
is much more rough than in the case of the spraying of
ion-exchanged water. .fwdarw..DELTA.
The distribution of droplets is as dense as or more dense than in
the case of the spraying of ion-exchanged water.
.fwdarw..largecircle. {circle around (3)} Anti-dripping properties;
Under the same conditions as in the spraying for the evaluation of
the unevenness in the spray coating, a spraying was performed
several times until the overall surface of the frosted glass plate
(which was held vertically) was completely covered with the sprayed
composition. The anti-dripping properties of the sprayed
composition on the frosted glass plate (which was maintained in a
vertical position) was observed after every spraying and was
evaluated in accordance with the following criteria.
A dripping occurs even after only one spraying. .fwdarw.X
Although a dripping does not occur after the first spraying, a
dripping occurs after two or more sprayings are performed to
increase the thickness of the spray coating on the surface of the
frosted glass plate. .fwdarw..DELTA.
No dripping occurs even after the spraying is repeated until the
overall surface of the frosted glass plate was completely covered
with the sprayed composition. .fwdarw..largecircle. {circle around
(4)} Coating formation ability; A spraying was performed several
times under the same conditions as in the spraying for the
evaluation of the unevenness in the spray coating. The spray
coating formed on the surface of the frosted glass plate was, as
such, allowed to dry at room temperature to obtain a coated glass.
The state of the surface of the obtained coating on the glass was
observed and was evaluated in accordance with the following
criteria.
The surface of the coating exhibits high uniformity (no rough
feel), and even when the surface of the coating is rubbed by
finger, the coating cannot be peeled off. .fwdarw..largecircle.
The surface of the coating exhibits a markedly rough feel; or even
if the surface of the coating exhibits high uniformity, when the
surface of the coating is rubbed by finger, the coating can be
easily peeled off. .fwdarw.X
EXAMPLES 1 TO 7
With respect to a spraying composition comprising a cellulose/water
dispersion, the spraying properties were examined as follows.
(1) Preparation of a Cellulose/Water Dispersion
A sheet form of purified pulp was cut into chips having a size of 5
mm.times.5 mm A, to thereby obtain a raw material pulp having a
degree of polymerization of 760 (hereinbelow referred to simply as
a "purified pulp"). The purified pulp was dissolved in a 65% by
weight aqueous sulfuric acid solution at -5.degree. C. so as to
obtain a cellulose concentration of 5% by weight, thereby obtaining
a transparent and viscous cellulose dope. The cellulose dope was
poured, while stirring, into water (at 5.degree. C.) in an amount
about 2.5 times the weight of the cellulose dope, to thereby
aggregate the cellulose to form a floc, thereby obtaining a
suspension of a floc form of solids. The obtained suspension was
subjected to hydrolysis at 85.degree. C. for 20 minutes, and then
the aqueous sulfuric acid solution as a dispersion medium was
removed from the suspension by vacuum filtration using a
fritted-glass filter, to obtain solids. The obtained solids were
repeatedly subjected to washing until the pH value of the washings
became about 3 and then washed (neutralized) with a thin aqueous
ammonia solution having a pH value of about 11, followed by further
washing thereof with ion-exchanged water, to thereby obtain a white
opaque, gel-like product having a cellulose content of 6.0% by
weight. The gel-like product was diluted with ion-exchanged water
so as to adjust the cellulose content thereof to 4.0% by weight.
The resultant diluted product was subjected to a treatment for
dispersing, at a revolution rate of 15,000 rpm for 10 minutes by
means of a homomixer (T. K. ROBO MICS.TM., manufactured and sold by
TOKUSHU KIKA KOGYO Co., Ltd., Japan), and then subjected 5 times to
a treatment for dispersing, under a pressure of 1.72.times.10.sup.8
Pa by means of an ultrahigh pressure homogenizer
(Microfluidizer.TM. Model M110-EH, manufactured and sold by Mizuho
Kogyo Kabushiki Kaisha, Japan), to thereby obtain a cellulose/water
dispersion (pH=6.7) exhibiting a high transparency. The obtained
cellulose/water dispersion having a cellulose content of 4.0% by
weight is hereinafter referred to as "sample A". FIG. 1 shows a
wide-angle X ray pattern of a dried product obtained from sample
A.
The cellulose of the sample A had an average degree of
polymerization of 38, a crystallinity such that X.sub.I was 0 and
X.sub.II was 0.18, and an average particle diameter of 0.3
.mu.m.
(2) Preparation of the Samples S1 to S7 and Evaluation of the
Spraying Properties
Ion-exchanged water was added to the sample A so as to prepare four
diluted samples having cellulose contents of 0.5% by weight, 1.0%
by weight, 1.5% by weight and 2.0% by weight, respectively. Each of
the diluted samples was individually subjected to a treatment for
dispersing, at a revolution rate of 15,000 rpm for 10 minutes by
means of a homomixer (T. K. ROBO MICS.TM., manufactured and sold by
TOKUSHU KIKA KOGYO Co., Ltd., Japan) to obtain four cellulose/water
dispersions which were spraying compositions used in the present
invention. These dispersions were, respectively, designated samples
"S1", "S2", "S3" and "S4" in the order from the sample having the
lowest cellulose content to the sample having the highest cellulose
content. The transmittances of these samples to visible rays having
a wavelength of 660 nm were 99% (S1), 98% (S2), 96% (S3) and 93%
(S4), as measured in the state in which they were individually
diluted with water to have a particulate cellulose concentration of
0.05% by weight. The maximum viscosity values (.eta..sub.max) of
the samples S1, S2, S3 and S4 at 25.degree. C. were
2.times.10.sup.3 mPas (S1), 2.times.10.sup.5 mPas (S2),
2.times.10.sup.6 mPas (S3) and 5 (107 mPas (S4). FIGS. 2 and 3 are
graphs which show specific examples of measurement data for
evaluating the maximum viscosity (.eta..sub.max) defined in the
present invention, wherein the data was obtained, with respect to
the sample S3 by using a cone-plate type rotating viscometer.
A commercially available crystallite cellulose/water dispersion,
namely Ceolus FP-03.TM. (cellulose content: 10% by weight,
manufactured and sold by ASAHI KASEI CORPORATION, Japan) was
diluted with ion-exchanged water so as to adjust the cellulose
content thereof to 4.0% by weight, and then subjected to a
treatment for dispersing, at a revolution rate of 15,000 rpm for 10
minutes by means of a homomixer (T. K. ROBO MICS.TM., manufactured
and sold by TOKUSHU KIKA KOGYO Co., Ltd., Japan) to obtain a
cellulose/water dispersion (sample S5).
Next, Ceolus FP-03.TM. was diluted with ion-exchanged water so as
to adjust the cellulose content thereof to 2.0% by weight, and then
subjected to a treatment for dispersing, at a revolution rate of
15,000 rpm for 10 minutes by means of a homomixer (T. K. ROBO
MICS.TM., manufactured and sold by TOKUSHU KIKA KOGYO Co., Ltd.,
Japan) to obtain a cellulose/water dispersion. The obtained
cellulose/water dispersion was subjected 5 times to a treatment for
dispersing, under a pressure of 1.72.times.10.sup.8 Pa by means of
an ultrahigh pressure homogenizer (Microfluidizer.TM. Model
M110-EH, manufactured and sold by Mizuho Kogyo Kabushiki Kaisha,
Japan), to thereby obtain a white opaque cellulose/water dispersion
(sample S6).
Each of the celluloses of the samples S5 and S6 had a degree of
polymerization of 150 and a crystallinity such that X.sub.I was
0.65 and X.sub.II was 0. The celluloses of the samples S5 and S6
had average particle diameters of 5.2 .mu.m and 0.2 .mu.m,
respectively. The transmittances of the samples 5S and S6 to
visible rays having a wavelength of 660 nm were, respectively, 0.3%
and 26%, as measured in the state in which they were individually
diluted with water to have a particulate cellulose concentration of
0.05% by weight. The maximum viscosity values (.eta..sub.max) of
the samples S5 and S6 were 6.times.10.sup.4 mPas and
7.times.10.sup.4 mPas, respectively.
A commercially available cuprammonium rayon long fiber was finely
cut into a length of 1 mm, and the resultant was hydrolyzed in a
30% aqueous sulfuric acid solution at 80.degree. C., for 2 hours to
obtain a dispersion. The obtained dispersion was subjected to
filtration using a fritted-glass filter, followed by repetition of
washing with ion-exchanged water until the pH value of the washings
became about 4, thereby obtaining a cake. The obtained cake was
neutralized by means of a diluted ammonia aqueous solution having a
pH value of about 11, followed by washing thereof with
ion-exchanged water to thereby obtain a dispersion. The obtained
dispersion was diluted with ion-exchanged water so as to adjust the
cellulose content thereof to 2.0% by weight and then subjected to a
preliminary treatment for dispersing, at a revolution rate of
15,000 rpm for 10 minutes by means of a homomixer (T. K. ROBO
MICS.TM., manufactured and sold by TOKUSHU KIKA KOGYO Co., Ltd.,
Japan), and then subjected 5 times to a treatment for dispersing,
under a pressure of 1.72.times.10.sup.8 Pa by means of an ultrahigh
pressure homogenizer (Microfluidizer.TM. Model M110-EH,
manufactured and sold by Mizuho Kogyo Kabushiki Kaisha, Japan), to
thereby obtain a slightly whitish opaque cellulose/water dispersion
having a cellulose content of 2.0% by weight (sample 7).
The cellulose of the sample 7 had an average degree of
polymerization of 42, a crystallinity such that X.sub.I was 0 and
X.sub.II was 0.52, and an average particle diameter of 0.3 .mu.m.
The transmittance of the sample S7 to visible rays having a
wavelength of 660 nm was 65%, as measured in the state in which
sample S7 was diluted with water to have a particulate cellulose
concentration of 0.05% by weight. The maximum viscosity value
(.eta..sub.max) of the sample S7 was 8.times.10.sup.4 mPas.
Each of the thus-obtained dispersions (samples 1 to 7) was
individually packed in a commercially available dispenser-type
spray container device having a volume of 50 ml (manufactured and
sold by SANPLATEC Corp., Japan), and subjected to evaluation of the
spraying properties. The results are shown in Table 1.
It was found that all of the samples 1 to 7 exhibited excellent
spraying properties.
It is necessary for the spraying composition used in the present
invention to have an advantage in that, after spraying and drying,
the spraying composition can form an excellent coating. Therefore,
the coating formation abilities (after drying) of the samples 1 to
7 were examined. It was found that each of the coatings formed from
the samples S1 to S7 exhibited high uniformity (no rough feel) and
that, even when each of the coatings was rubbed by finger, the
coatings could not be peeled off, thereby confirming that a strong
coating was formed. The results are shown in Table 1.
COMPARATIVE EXAMPLES 1 TO 7
(Preparation of the Samples H1 to H7 and Evaluation of the Spraying
Properties)
As described hereinbelow, evaluation of spraying properties was
performed with respect to each of a cellulose dispersion which did
not satisfy the requirements of the present invention, an aqueous
polymer solution, and a microparticle dispersion.
A crystalline cellulose powder, namely Avicel PH-101.TM. was
dispersed in ion-exchanged water so that the resultant dispersion
had a cellulose content of 5% by weight, and the obtained
dispersion was subjected to a treatment for dispersing, at a
revolution rate of 15,000 rpm for 10 minutes by means of a
homomixer (T. K. ROBO MICS.TM., manufactured and sold by TOKUSHU
KIKA KOGYO Co., Ltd., Japan) to obtain a white cellulose/water
dispersion (sample H1).
The sample H1 exhibited a property such that when the sample H1 was
allowed to stand for several minutes, a transparent supernatant was
formed therein, indicating that the sample H1 was an inhomogeneous,
incomplete dispersion.
The cellulose of the sample Hi had an average degree of
polymerization of 150, a crystallinity such that X.sub.I was 0.64
and X.sub.II was 0, and an average particle diameter of 21 .mu.m.
The transmittance of the sample H1 to visible rays having a
wavelength of 660 nm was almost 0%, as measured in the state in
which the sample H1 was diluted with water to have a particulate
cellulose concentration of 0.05% by weight. The maximum viscosity
value (.eta..sub.max) of the sample H1 was 1.times.10.sup.3 mPas.
With respect to the measurement of the transmittance and the
.eta..sub.max value of the sample H1, the sample H1 was strongly
shaken just before the measurement, and the measurement was then
performed quickly.
Further, as additional comparative samples, aqueous solutions and
aqueous dispersions were prepared by a method in which each of the
following raw materials: a crosslinked acrylic copolymer (namely
Carbopol 940.TM. (sold by Chugai Boyeki Co., Ltd., Japan)), a
polyacrylamide (average molecular weight: 9,000,000 to 10,000,000;
manufactured and sold by KISHIDA CHEMICAL CO., LTD., Japan), and a
particulate synthetic smectite (namely SMECTON SA2.TM.
(manufactured and sold by KUNIMINE INDUSTRY, Japan)), was
individually dissolved or dispersed in ion-exchanged water used as
a solvent or a dispersion medium so that, from each raw material,
two aqueous mixtures were obtained which had raw material contents
of 0.5% by weight and 1.5% by weight, respectively.
With respect to Carbopol and a polyacrylamide, the aqueous
solutions thereof were prepared by the conventional method
(wherein, in the preparation of the aqueous solutions of Carbopol,
after dissolving Carbopol in water, neutralization with a diluted
aqueous ammonia was performed). The 0.5% by weight aqueous solution
of Carbopol (in the form of a gel) was designated "sample H2", and
the 1.5% by weight aqueous solution of Carbopol (in the form of a
gel) was designated "sample H3". The 0.5% by weight aqueous
solution of polyacrylamide (in the form of a solution) was
designated "sample H4", and the 1.5% by weight aqueous solution of
polyacrylamide (in the form of a solution) was designated "sample
H5".
With respect to the use of SMECTON SA2.TM., SMECTON SA2.TM. was
diluted with ion-exchanged water so that the resultant mixtures had
SMECTON SA2.TM. concentrations of 0.5% by weight and 1.5% by
weight, respectively, and then the obtained mixtures were
individually subjected to a treatment for dispersing, at a
revolution rate of 15,000 rpm for 10 minutes by means of a
homomixer (T. K. ROBO MICS.TM., manufactured and sold by TOKUSHU
KIKA KOGYO Co., Ltd., Japan) to obtain transparent aqueous
dispersions.
The 0.5% by weight SMECTON SA2.TM. dispersion was designated
"sample H6" and the 1.5% by weight SMECTON SA2.TM. dispersion was
designated "sample H7". The transmittances of the samples H2 to H7
to visible rays having a wavelength of 660 nm were 99% or more (H2,
H3, H4 and H5), 89% (H6) and 72% (H7), as measured in the state in
which the samples were individually diluted with water to have a
raw material concentration of 0.05% by weight. The maximum
viscosity values (.eta..sub.max) of the samples H2 to H7 at
25.degree. C. were 3.times.10.sup.6 mPas (H2), 1.times.10.sup.7
mPas (H3), 4.times.10.sup.2 mPas (H4), 4.times.10.sup.4 mPas (H5),
3.times.10.sup.2 mPas (H6) and 1.times.10.sup.6 mPas (H7). Each of
the thus obtained dispersions or aqueous solutions (H1 to H7) was
individually packed in a commercially available dispenser type
spray container device having a volume of 50 ml (manufactured and
sold by SANPLATEC Corp., Japan), and subjected to evaluation of the
spraying properties. The results are shown in Table 1.
In the case of the sample H1, which was a dispersion containing a
particulate cellulose having a relatively large particle diameter,
the particulate cellulose caused a temporary clogging of the
nozzle, and therefore a stable spraying could not be achieved.
Also, the unevenness in the spray coating was large. Further, with
respect to the aqueous solutions which contained Carbopol or
polyacrylamide dispersed (dissolved) therein in the molecular form,
a spraying from the spray container device could not be performed
irrespective of the concentrations of these aqueous solutions, and
therefore it was shown that the viscous aqueous solutions
containing Carbopol or polyacrylamide were unsuitable as a spraying
composition. On the other hand, the dispersion of SMECTON exhibited
good spraying properties; however, from the viewpoint of the
anti-dripping properties, the dispersion of SMECTON was not
satisfactory. When the coating formation abilities of the samples
H1 to H7 were examined by substantially the same method as in the
evaluation of the samples S1 to S7, it was found that the sample H1
formed a white coating giving a markedly rough feel, and that the
samples H2 to H7 formed coatings which were transparent and which
exhibited a high uniformity. When these coatings were rubbed by
finger, although no peeling off was observed in the case of the
coatings formed from the samples H1 to H5, the coatings formed from
the samples H6 and H7 were easily peeled off from the glass plate
and the resultant powdery debris of the coatings stuck to the
finger. Thus, it was found that although the dispersion of the
SMECTON exhibited good spraying properties, the coating formation
ability of the dispersion of the SMECTON was very poor, as compared
to the spraying composition used in the present invention. The
results are shown in Table 1.
EXAMPLE 8 AND COMPARATIVE EXAMPLE 8
In order to show the difference between the spraying composition
used in the present invention and a dispersion of the synthetic
smectite, the following experiments were performed.
Ion-exchanged water and ethanol were added to the above-mentioned
sample A so that the resultant mixture had a cellulose content of
2% by weight and an ethanol/water weight ratio of 30/70 (g/g), and
then the obtained mixture was subjected to a treatment for
dispersing, at a revolution rate of 15,000 rpm for 10 minutes by
means of a homomixer (T. K. ROBO MICS.TM., manufactured and sold by
TOKUSHU KIKA KOGYO Co., Ltd., Japan) to thereby obtain a
transparent aqueous dispersion (sample S8).
Likewise, ion-exchanged water and ethanol were added to SMECTON
SA2.TM. so that the resultant mixture had a SMECTON SA2.TM. content
of 2% by weight and an ethanol/water weight ratio of 30/70 (g/g),
and then the obtained mixture was subjected to a treatment for
dispersing, at a revolution rate of 15,000 rpm for 10 minutes by
means of a homomixer (T. K. ROBO MICS.TM., manufactured and sold by
TOKUSHU KIKA KOGYO Co., Ltd., Japan) to thereby obtain a white
opaque aqueous dispersion (sample H8).
The transmittances of the thus-obtained samples S8 and H8 to
visible rays having a wavelength of 660 nm were 92% (S8) and 2%
(H8), as measured in the state in which the samples S8 and H8 were
individually diluted with water to have a particulate cellulose
concentration of 0.05% by weight and a SMECTON SA2.TM.
concentration of 0.05% by weight, respectively. The maximum
viscosity values (.eta..sub.max) of the samples S8 and H1 at
25.degree. C. were 6.times.10.sup.7 mPas (S8) and 1.times.10.sup.6
mPas (H8).
Each of the samples S8 and H8 was individually packed in a
commercially available dispenser type spray container device having
a volume of 50 ml (manufactured and sold by SANPLATEC Corp.,
Japan), and subjected to evaluation of the spraying properties. The
results are shown in Table 2. Each of the samples S8 and H8
exhibited excellent spraying properties.
Next, the coating formation abilities of the samples S8 and H8 were
examined by the above-mentioned method. It was found that the
coating formed from the sample S8 was transparent, and even when
the coating was rubbed by finger, no peeling off of the coating
occurred. On the other hand, the coating formed from the sample H8
was opaque and also rough and non-uniform, where the roughness and
non-uniformity indicated that weak agglomeration of SMECTON SA2.TM.
occurred during the drying of the sprayed sample H8 on the glass
plate.
Further, when the coating formed from the sample H8 was rubbed by
finger, the white opaque coating was easily peeled off from the
glass plate and the resultant powdery debris of the coating stuck
to the finger. For comparison with the coating formed from the
sample H8, the coating formed from a SMECTON/water dispersion
having a SMECTON content of 1.5% by weight and exhibiting a
relatively high transparency, was observed (wherein the coating was
obtained in Comparative Example 7). It was found that the coating
obtained in Comparative Example 7 exhibited high transparency
(although the thickness of the coating was non-uniform because of
the occurrence of dripping in accordance with the lapse of time);
however, when this transparent coating was rubbed by finger, a
powder of smectite easily came off, as in the case of the sample
H8. Thus, it was found that a synthetic somectite exhibits a lower
agglomeration during the drying of the wet coating, than in the
case of a particulate cellulose, and therefore it is difficult for
a synthetic smectite dispersion to form a continuous dry coating,
that is, a synthetic smectite dispersion has almost no coating
formation ability.
Thus, the following was found. When a dispersion of an inorganic
particle, such as a synthetic smectite, is used as a spraying
composition, dripping (after spraying) can be prevented to some
degree. However, the dispersion of an inorganic particle has a
defect in that when a dispersion medium having high general-purpose
properties, such as alcohol, is added to the inorganic particle,
agglomeration of the inorganic particle occurs, and also a coating
formed from the dispersion becomes non-uniform and can be easily
peeled off from the glass plate, making it impossible to produce a
functional durable coating.
EXAMPLES 9 TO 11
In order to illustrate the composition for use in the present
invention containing an ionic compound as a functional additive,
the following experiments were performed. A composition for use in
the present invention was prepared containing, as a functional
additive, an ionic compound, namely betaine (N-trimethylglycin,
represented by the formula: (CH).sub.3 N.sup.+CH.sub.2CO.sup.-),
which is an amphoteric humectant. The composition was evaluated
with respect to the stability, spraying properties and coating
formation ability thereof. In the experiments, three compositions
were prepared as follows:
sample S9: cellulose: 1.5% by weight betaine: 0.5% by weight water:
balance
sample S10: cellulose: 1.5% by weight betaine: 0.5% by weight
ethanol: 10% by weight water: balance
sample S11: cellulose: 1.5% by weight betaine: 6% by weight water:
balance
TABLE-US-00001 sample S9: cellulose: 1.5% by weight betaine: 0.5%
by weight water: balance sample S10: cellulose: 1.5% by weight
betaine: 0.5% by weight ethanol: 10% by weight water: balance
sample S11: cellulose: 1.5% by weight betaine: 6% by weight water:
balance
The samples were prepared by the following method.
Predetermined amounts of a betaine, an ethanol (only for producing
sample S10) and ion-exchanged water were added to the
above-mentioned sample A in accordance with the above-mentioned
formulations. The resultant mixtures were individually subjected to
a treatment for dispersing, at a revolution rate of 10,000 rpm and
at room temperature (under cooling) for 10 minutes, by means of a
vacuum emulsification equipment (PVQ-3UN, manufactured and sold by
Mizuho Kogyo Kabushiki Kaisha, Japan), followed by vacuum
defoaming, thereby obtaining the samples as mentioned above. The
obtained three samples S9 to S11 were evaluated, and it was found
that the maximum viscosity values (.eta..sub.max) of samples S9 to
S11 at 25.degree. C. were 3.times.10.sup.5 mPas (S9),
8.times.10.sup.5 mPas (S10) and 7.times.10.sup.5 mPas (S18),
respectively; and the transmittances of samples S9 to S11 to
visible rays having a wavelength of 660 nm were 96% (S9), 91% (S10)
and 93% (S11), as measured in the state in which the samples were
individually diluted with water to have a particulate cellulose
concentration of 0.05% by weight.
with respect to homogeneity and whether or not phase separation
occurred, each sample was examined both immediately after the
preparation thereof and after each sample was allowed to stand
still for 24 hours at room temperature from the preparation
thereof. As a result, it was found that each sample was homogeneous
and exhibited no phase separation at any time point the examination
was made. Thus, it was found that the three compositions as
mentioned above had desired properties with respect to homogeneity
and stability. Further, samples S9 to S11 were individually
examined with respect to the state of spray, unevenness in spray
coating, and anti-dripping properties (after spraying), in
substantially the same manner as in the evaluation of samples S1 to
S8. As a result, it was found that each sample exhibited excellent
properties (evaluation symbol .largecircle.) in all these items of
evaluation. Further, samples S9 to S11 were individually evaluated
with respect to the coating forming ability thereof in
substantially the same manner as in Examples 1 to 7. As a result,
it was found that each of the coatings formed from samples S9 to
S11 exhibited high uniformity (no rough feel) and that, even when
each of the coatings was rubbed by finger, the coatings could not
be peeled off, thereby confirming that a strong coating was
formed.
From these results, it was found that the three compositions as
mentioned above can be advantageously used because they exhibit
excellent properties with respect to all of stability, spraying
properties and coating formation ability.
EXAMPLE 12
Using the above-mentioned sample A, a spray pack was produced
containing a cosmetic whitening gel spray composition having a
whitening effect, which had the following formulation:
TABLE-US-00002 dipropylene glycol (humectant): 5.0% by weight
polyethylene glycol (humectant): 5.0% by weight ethanol: 10.0% by
weight polyoxyethylene sorbitan monostearate (surfactant): 1.0% by
weight sorbitan monooleate (surfactant): 0.5% by weight oleyl
alcohol (emollient): 0.5% by weight placenta extract (medicine):
0.2% by weight vitamin E acetate (medicine): 0.2% by weight a
perfume, an antiseptic agent and appropriate amounts an
anti-discoloration agent: sample A: 37.5% by weight purified water:
39.3% by weight
(Production Method)
Purified water was added to sample A. The resultant mixture was
subjected to a treatment for dispersing, at a revolution rate of
7,000 rpm by means of a homomixer (T.K. ROBO MICS.TM., manufactured
and sold by Tokushu Kika Kogyo Co., Ltd., Japan), and the
humectants and anti-discoloration agent were consecutively added to
and dissolved in the mixture while effecting the treatment for
dispersing, followed by a further treatment for dispersing for 10
minutes, thereby obtaining an aqueous gel. On the other hand, the
emollient, medicines and antiseptic agent were dissolved into
ethanol, and the resultant solution was added to the
above-mentioned aqueous gel, and the resultant mixture was
subjected to a microemulsification at a revolution rate of 10,000
rpm by means of the homomixer, followed by deaeration and
filtration, thereby obtaining a translucent gel-like composition.
The obtained translucent gel-like composition was packed in a 50 ml
volume dispenser type spray container device (manufactured and sold
by SANPLATEC Corp., Japan). The obtained gel-like composition is
hereinafter referred to as "sample S12". The transmittance of
sample S12 to visible rays having a wavelength of 660 nm was 34%,
as measured in the state in which sample S12 was diluted with water
to have a particulate cellulose concentration of 0.05% by weight.
The maximum viscosity value (.eta.max) of sample S12 at 25.degree.
C. was 1.times.10.sup.7 mPas.
(Evaluation)
Sample S12 was examined with respect to the state of spray,
unevenness in spray coating, and anti-dripping properties (after
spraying). As a result, it was found that sample S12 exhibited
excellent properties (evaluation symbol .largecircle.) in all these
items of evaluation. Further, it was found that sample S12 was
homogeneous and exhibited no phase separation for a long time (for
3 months at 30.degree. C.), showing that sample S12 had high
stability. In order to confirm the safety of the gel-like
composition, an experiment was conducted as follows. Sample S12 was
sprayed over an upper arm of each of 10 healthy volunteers, and a
closed patch test was performed for 24 hours to investigate whether
or not a skin irritation was caused by the sprayed gel-like
composition. The results of the test were classified into the
following three degrees: .largecircle.=no irritation was caused,
.DELTA.=slight irritation, if any, was caused (or difficult to
judge), and X=irritation was caused. As a result, it was found that
with respect to all of the 10 persons, the test results were:
.largecircle.=no irritation was caused, thereby confirming the high
safety of the gel-like composition. Further, the gel-like
composition was sprayed onto the face of each of the
above-mentioned 10 healthy volunteers, in order to survey what
sensation was produced in the 10 persons immediately after the
spraying. In a questionnaire performed after the spraying, all 10
persons answered that they got excellent sensation, i.e., a smooth
and refreshing feel.
EXAMPLE 13
Using the above-mentioned sample A, a spray pack was produced
containing an emollient lotion spraying composition which serves as
a moisturizing emollient emulsion, wherein the spraying composition
had the following formulation:
TABLE-US-00003 cetyl alcohol (oil component): 1.0% by weight
beeswax (oil component): 0.5% by weight vaseline (oil component):
2.0% by weight squalane (oil component): 6.0% by weight
dimethylpolysiloxane (oil component): 2.0% by weight ethanol: 5.0%
by weight glycerol (humectant): 2.0% by weight 1,3-butylen glycol
(humectant): 3.0% by weight polyethylene glycol (10) monooleate
(surfactant): 0.5% by weight glycerol monostearate (surfactant):
1.0% by weight an antiseptic agent and a perfume: appropriate
amounts sample A: 30.0% by weight purified water: 29.0% by
weight
(Production Method)
The humectants were added to purified water, and the resultant
aqueous mixture was stirred at a revolution rate of 7,000 rpm by
means of a homomixer (T.K. ROBO MICS.TM., manufactured and sold by
Tokushu Kika Kogyo Co., Ltd., Japan) while heating until the
temperature of the aqueous mixture reached 70.degree. C. On the
other hand, the surfactant and antiseptic agent were added to the
oil components, and the resultant oily mixture was heated to
70.degree. C. The oily mixture at 70.degree. C. was added to the
aqueous mixture in the homomixer while stirring, thereby effecting
a preliminary emulsification, thereby obtaining a preliminary
emulsion. The revolution rate of the homomixer was changed to 9,000
rpm and then sample A and ethanol were added to the preliminary
emulsion, and the resultant was subjected to a treatment for
dispersing, at a revolution rate of 9,000 rpm for 10 minutes,
thereby obtaining a white gel-like liquid. The obtained white
gel-like liquid was then subjected to deaeration and filtration and
then cooled, thereby obtaining a spraying composition. The obtained
composition was packed in a 50 ml volume dispenser type spray
container device (manufactured and sold by SANPLATEC Corp., Japan).
The obtained composition is hereinafter referred to as "sample
S13". The transmittance of sample S13 to visible rays having a
wavelength of 660 nm was 2%, as measured in the state in which
sample S13 was diluted with water to have a particulate cellulose
concentration of 0.05% by weight. The maximum viscosity value
(.eta..sub.max) of sample S13 at 25.degree. C. was 3.times.10.sup.6
mPas.
(Evaluation)
Sample S13 was examined with respect to the state of spray,
unevenness in spray coating, and anti-dripping properties (after
spraying). As a result, it was found that sample S13 exhibited
excellent properties (evaluation symbol .largecircle.) in all these
items of evaluation. Further, it was found that sample S13 was
homogeneous and exhibited no phase separation for a long time (for
3 months at 30.degree. C.), showing that sample S13 had high
stability. In order to confirm the safety of sample S13, an
experiment was conducted as follows. Sample S13 was sprayed over an
upper arm of each of 10 healthy volunteers, and a closed patch test
was performed for 24 hours to investigate whether or not a skin
irritation was caused by the sprayed gel-like composition. The
results of the test were classified into the following three
degrees: .largecircle.=no irritation was caused, .DELTA.=slight
irritation, if any, was caused (or difficult to judge), and
X=irritation was caused. As a result, it was found that with
respect to 9 persons, the test results were: .largecircle.=no
irritation was caused, and 1 person gave test results such that the
evaluation symbol was .DELTA., thereby confirming the high safety
of the gel-like composition.
Further, the gel-like composition was sprayed onto the face of each
of the above-mentioned 10 healthy volunteers, in order to survey
what sensation was produced in the 10 persons immediately after the
spraying. In a questionnaire performed after the spraying, all 10
persons answered that they got excellent sensation, i.e., a smooth
and refreshing feel.
EXAMPLE 14 AND COMPARATIVE EXAMPLE 9
Using the above-mentioned sample A, a spray pack was produced in
which an aerosol shaving foam spraying composition having the
below-mentioned formulation (1) was packed in accordance with the
below-mentioned packing formulation (2).
(1) Formulation of the Spraying Composition
TABLE-US-00004 stearic acid (oil component): 4.5% by weight coconut
oil fatty acid (oil component): 1.5% by weight glycerin
monostearate (surfactant): 5.0% by weight glycerol (humectant):
10.0% by weight triethanolamine (alkali) 4.0% by weight perfume: an
appropriate amount sample A: 25.0% by weight (for Example 14)
sample A: not added (for Comparative Example 9) purified water:
50.0% by weight (for Example 14) purified water: 75.0% by weight
(for Comparative Example 9)
(2) Packing Formulation (Common to the Example and Comparative
Example)
TABLE-US-00005 spraying composition: 96.0% by weight LPG
(propellant gas): 4.0% by weight
(Production Method)
Glycerol and triethanolamine were added to purified water, and the
resultant aqueous mixture (aqueous phase) was heated to and
maintained at 70.degree. C. On the other hand, the remainder of the
above-mentioned ingredients were mixed together and heated, and the
resultant oily mixture (oil phase) was heated to and maintained at
70.degree. C. The obtained oil phase was added to the obtained
aqueous phase, and the resultant mixture was subjected to a
treatment for reaction and emulsification, by stirring at a
revolution rate of 8,000 rpm by means of a homomixer (T.K. ROBO
MICS.TM., manufactured and sold by Tokushu Kika Kogyo Co., Ltd.,
Japan). The resultant emulsion was cooled to 30.degree. C. Then,
only in the case of Example 14, sample A was added to the emulsion
while stirring at a revolution rate of 8,000 rpm, and the resultant
mixture was subjected to a treatment for dispersing for 10 minutes,
thereby obtaining an emulsion. In both of the Example and
Comparative Example, the obtained emulsions were individually
subjected to deaeration and filtration, thereby obtaining white
viscous emulsified compositions. Each of the obtained compositions
was individually packed in an aerosol container device in an amount
as specified above, and a valve was fitted on the container device,
and then the propellant gas in an amount as specified above was
introduced in the container device, to thereby obtain an aerosol
spray pack. The spraying compositions obtained in Example 14 and
Comparative Example 9 are hereinafter referred to as "sample S14"
and "sample H9", respectively. The transmittances of samples S14
(containing cellulose) and H9 (containing no cellulose) to visible
rays having a wavelength of 660 nm were both less than 1%, as
measured in the state in which the samples were diluted with water
to have oil concentrations which are the same with respect to both
of the samples, wherein sample S14 has a particulate cellulose
concentration of 0.05% by weight. The maximum viscosity values
(.eta..sub.max) of samples S14 and H9 at 25.degree. C. were
2.times.10.sup.6 mPas (S14) and 5.times.10.sup.3 mPas (H9).
(Evaluation)
When samples S14 and H9 were evaluated with respect to the spraying
properties thereof, both samples produced a good foam. 5 Minutes
after the spraying, a comparison was made between the volumes of
the two foams produced from the samples. It was found that the
volume of the foam produced from sample H9 had reduced to a volume
which is less than 1/2 of the original volume thereof, whereas the
foam produced from sample S14 retained its volume as measured
immediately after the spraying. Thus, it was shown that the foam
obtained in Example 14 exhibits an extremely high retention. Both
samples exhibited an excellent fixation to the skin surface. It was
also found that the spraying properties of both samples were stable
for a long time (for 3 months at 30.degree. C.). Further, an
experiment was performed in which each of these samples was
individually sprayed onto the chin of each of 10 healthy volunteers
and the resultant foam was used as a shaving foam, in order to
survey what sensation was produced in the 10 persons using the
shaving foam. In a questionnaire performed after the experiment,
all 10 persons answered that the foam produced from sample S14 gave
excellent sensation, and 7 persons answered that the foam produced
from sample H9 gave excellent sensation. Thus, it was found that
sample S14 is superior to sample H9 in the retention of foam and
the sensation produced when used.
EXAMPLE 15
Using the above-mentioned sample A, a spray pack was produced in
which an aerosol nonsteroidal anti-inflammatory analgesic spraying
composition having the below-mentioned formulation (1) was packed
in accordance with the below-mentioned packing formulation (2).
(1) Formulation of the Spraying Composition
TABLE-US-00006 ketoprofen (active ingredient): 0.3% by weight
ethanol: 30.0% by weight propylene glycol (water-soluble additive):
1.0% by weight cetyl alcohol (oil component): 0.5% by weight
palmitic acid (oil component): 0.5% by weight isopropyl myristate
(oil component): 0.1% by weight dimethylpolysiloxane (oil
component): 0.1% by weight polyoxyethylene(50)-hardened castor oil
(surfactant): 0.2% by weight citric acid (pH adjustor): 0.06% by
weight sample A: 18.8% by weight purified water: 48.4% by
weight
(2) Packing Formulation
TABLE-US-00007 spraying composition: 50.0% by weight LPG
(propellant gas): 50.0% by weight
(Production Method)
Purified water was added to sample A. The resultant mixture was
subjected to a treatment for dispersing, at a revolution rate of
7,000 rpm by means of a homomixer (T.K. ROBO MICS.TM., manufactured
and sold by Tokushu Kika Kogyo Co., Ltd., Japan), and the
water-soluble additive was added to and dissolved in the mixture
while effecting the treatment for dispersing, followed by a further
treatment for dispersing for 10 minutes, thereby obtaining a
slightly viscous transparent dispersion. On the other hand, the
surfactant, oil components and active ingredient were dissolved
into ethanol, and the resultant solution was added to the
above-mentioned transparent dispersion, and the resultant mixture
was subjected to a microemulsification at a revolution rate of
10,000 rpm by means of the homomixer, followed by deaeration and
filtration, thereby obtaining a highly transparent, viscous
composition. The obtained composition was packed in an aerosol
container device in an amount as specified above, and a valve was
fitted on the container device, and the propellant gas in an amount
as specified above was introduced into the container device, to
thereby obtain an aerosol spray pack. The spraying composition
obtained in Example 15 is hereinafter referred to as "sample S15".
The transmittance of sample S15 to visible rays having a wavelength
of 660 nm was 84%, as measured in the state in which sample S12 was
diluted with water to have a particulate cellulose concentration of
0.05% by weight. The maximum viscosity value (.eta..sub.max) of
sample S15 at 25.degree. C. was 8.times.10.sup.3 mPas.
(Evaluation)
Sample S15 was examined with respect to the state of spray,
unevenness in spray coating, and anti-dripping properties (after
spraying). As a result, it was found that sample S15 exhibited
excellent properties (evaluation symbol .largecircle.) in all these
items of evaluation. Further, it was found that sample S15
exhibited substantially the same excellent properties even after it
was stored for a long time (for 3 months at 30.degree. C.), showing
that sample S15 had high storage stability. Further, an experiment
was performed for 10 days, in which 10 healthy persons perform an
exercise every day, and sample S15 was used by the 10 healthy
persons after the exercise in order to survey the sensation
produced immediately after the spraying of sample S15 as well as
the anti-inflammatory effects of sample S15 on the muscles. After
the 10-day experiment, a questionnaire was given. In the
questionnaire, all 10 persons answered that they got excellent
sensation, i.e., a smooth and refreshing feel, and 8 persons
answered that the anti-inflammatory effects of sample S15 were very
high.
EXAMPLE 16
Using the above-mentioned sample A, a spray pack was produced
comprising a trigger type container device and, packed therein, a
detergent spraying composition having the following
formulation:
TABLE-US-00008 polyoxyethylene(13)nonyl phenyl ether 5.0% by weight
(surfactant): ethanol: 5.0% by weight antiseptic agent: an
appropriate amount sample A: 37.5% by weight purified water: 52.5%
by weight
(Production Method)
Purified water was added to sample A. The resultant mixture was
subjected to a treatment for dispersing, at a revolution rate of
7,000 rpm for 10 minutes by means of a homomixer (T.K. ROBO
MICS.TM., manufactured and sold by Tokushu Kika Kogyo Co., Ltd.,
Japan), and the surfactant was added to the mixture, and then
ethanol having the antiseptic agent dissolved therein was added
thereto, followed by a further treatment for dispersing for 10
minutes. Thereafter, the resultant mixture was subjected to
deaeration and filtration, thereby obtaining a transparent gel-like
composition. The obtained composition was packed in a 500 ml volume
trigger type spray container device (CANIONSPRAY.TM., manufactured
and sold by SANPLATEC Corp., Japan). The obtained composition is
hereinafter referred to as "sample S16". The transmittance of
sample S16 to visible rays having a wavelength of 660 nm was 92%,
as measured in the state in which sample S16 was diluted with water
to have a particulate cellulose concentration of 0.05% by weight.
The maximum viscosity value (.eta..sub.max) of sample S16 at
25.degree. C. was 3.times.10.sup.6 mPas.
(Evaluation)
Sample S16 was examined with respect to the state of spray,
unevenness in spray coating, and anti-dripping properties (after
spraying). As a result, it was found that sample S16 exhibited
excellent properties (evaluation symbol .largecircle.) in all these
items of evaluation. Further, it was found that sample S16 was
homogeneous and exhibited no phase separation for a long time (for
3 months at 30.degree. C.), showing that sample S16 had high
stability.
Further, the following experiment was performed. A vertical surface
of a fixed porcelain (specifically, a urinal) was stained with an
oily substance. Sample S16 was sprayed onto the stain on the
vertical surface of the porcelain, and then the sprayed composition
and the stain were wiped off with a cloth. As a result, the
excellent cleaning effect of sample S16 was confirmed. Further, it
was found that, after the wiping off, the particulate cellulose of
sample S16 did not remain on the porcelain surface and, hence, the
porcelain surface did not lose its luster at all. In view of these
results, it is presumed that the cellulose (which is amphiphilic)
in the composition quite effectively functions for facilitating the
cleaning mechanism that water and the surfactant engulf and remove
the stain substance.
TABLE-US-00009 TABLE 1 Thickening agent State Unevenness Anti-
Coating (Concentration of in spray dripping formation Sample (% by
weight) spray coating properties ability S1 cellulose (0.5)
.largecircle. .largecircle. .DELTA. .largecircle. S2 cellulose
(1.0) .largecircle. .largecircle. .largecircle. .largecircle. S3
cellulose (1.5) .largecircle. .largecircle. .largecircle.
.largecircle. S4 cellulose (2.0) .largecircle. .largecircle.
.largecircle. .largecircle. S5 cellulose (4.0) .largecircle.
.DELTA. .DELTA. .largecircle. S6 cellulose (2.0) .largecircle.
.DELTA. .DELTA. .largecircle. S7 cellulose (2.0) .largecircle.
.DELTA. .DELTA. .largecircle. H1 cellulose (5.0) X X X X H2
Carbopol 940 .TM. X cannot be cannot be X (0.5) evaluated evaluated
H3 Carbopol 940 .TM. X cannot be cannot be X (1.5) evaluated
evaluated H4 polyacrylamide .DELTA. X X X (0.5) H5 polyacrylamide X
cannot be cannot be X (1.5) evaluated evaluated H6 Smecton SA2 .TM.
.largecircle. .largecircle. .DELTA. X (0.5) H7 Smecton SA2 .TM.
.largecircle. .largecircle. .DELTA. X (1.5)
TABLE-US-00010 TABLE 2 Unevenness Anti- State of in spray dripping
Sample spray coating properties S8 .largecircle. .largecircle.
.largecircle. H8 .largecircle. .DELTA. .DELTA.
INDUSTRIAL APPLICABILITY
The spraying composition used in the present invention is
advantageous not only in that it has excellent spraying properties
but also, after the spraying, the sprayed composition (coating) has
excellent properties with respect to fixation to the surface
coated, anti-dripping properties, spreadability and finish
(uniformity of the coating). Therefore, the spray pack of the
present invention can be used in a wide variety of fields, such as
the fields of skincare products, hair care products, a medicine for
external use, a medicine for oral use, an insecticide, a fragrance,
a deodorizer, an antimicrobial agent, a sterilizer, a halitosis
deodorizer, a detergent, a paint, a coating agent for anti-fogging
treatment, a coating agent for anti-static treatment, and an
antiseptic agent. By appropriately adjusting the formulation of the
composition, it is possible to provide a foamable spraying
composition capable of producing a foam having very high stability
(very high retention) and provide a spraying composition having
very high safety. Further, by appropriately selecting the liquid
dispersion medium and other components of the composition, as long
as the selection is made so as not to spoil the excellent effects
of the composition, it is possible to provide not only spraying
compositions having conventional formulations, but also spraying
compositions having a wide variety of new aqueous formulations.
* * * * *